REACTIVE DISTILLATION METHOD AND SYSTEM

专利摘要:
reactive distillation method and system. a reactive distillation method comprises introducing a feed stream to a reactive distillation column, contacting the feed stream with one or more catalysts in the reactive distillation column during a distillation, and removing one or more higher alcohols during distillation from the reactive distillation column. reactive distillation as a downstream. the feed stream comprises one or more alpha hydrogen alcohols and the feed stream is reacted in the presence of the one or more catalysts to produce a reaction product comprising the one or more higher alcohols.
公开号:BR112015019704B1
申请号:R112015019704-3
申请日:2014-02-18
公开日:2021-09-14
发明作者:Sagar B. Gadewar；Brian Christopher Vicente；Peter K. Stoimenov；Vivek Julka
申请人:Rescurve, Llc；
IPC主号:

专利说明:

FUNDAMENTALS
[001] N-Butanol and ethyl acetate are commercially significant organic compounds having use in a wide variety of applications and which are produced in quantities exceeding 1 million tons per year. N-Butanol can be produced from many different reactions. The most common method for making n-butanol is hydroformylation. Propylene reacts with synthesis gas in cobalt or rhodium catalysts at high pressures to produce an aldehyde (butyraldehyde), which is then hydrogenated in a nickel catalyst to give an alcohol. Disadvantages of such a process include the high energy costs associated with the generation of syngas, the use of a potentially non-renewable feedstock (propylene and syngas are typically supplied from oil and natural gas, respectively) and the complexity of the process that requires multiple reactors and typically homogeneous hydroformylation catalysts.
[002] N-Butanol can also be produced from an aldol condensation reaction followed by hydrogenation. This method converts acetaldehyde to butanols, although the high toxicity and limited availability of acetaldehyde make such a process unattractive. Some processes, for example, U.S. Patent No. 1,992,480 and U.S. Patent No. 8,071,823 both of which are incorporated herein by reference in their entirety, utilize a gas phase reaction to provide butanol.
[003] Direct fermentation of sugars is another process for the production of n-butanol. As a bioprocess, this method suffers from long processing times and large separation requirements in addition to the need for specialized microbes needed to manufacture butanol directly from sugars.
[004] Ethyl acetate can also be produced from several different reactions. The most common method for making ethyl acetate is the esterification of acetic acid and ethanol. This reaction requires two supplies of raw material with associated storage or production facilities. In locations without a sufficient supply of reliable cheap acetic acid, this process may not be economically viable.
[005] Ethyl acetate can also be produced from the oxidation of ethanol on supported precious metal catalysts. The high cost of precious metal catalyst can also make this option uneconomical.
[006] The Tishchenko reaction (dimerization of aldehydes into esters) is another alternative process for the production of ethyl acetate. Dimerization of acetaldehydes results in ethyl acetate, however aldol condensation also occurs, resulting in by-products such as 2-butanone and 2-propanol, both of which form azeotropes with ethyl acetate. In addition, the Tishchenko reaction requires a supply of acetaldehyde, which may not be readily available and may be difficult to store and handle due to its high toxicity.
[007] 1-Hexanol and 1-octanol are both made industrially via the oligomerization of ethylene using aluminum triethyl, followed by oxidation of the aluminum alkyl intermediate. In this process, aluminum triethyl does not serve as a catalyst, but rather is a reagent that is not easily regenerated. In particular, the reaction scheme starts with metallic aluminum and results in the formation of aluminum oxide and/or hydroxide on completion of the reaction. Triethylaluminum is expensive as it requires metallic aluminum as a precursor. Aluminum triethyl is also a pyrophoric material and poses a risk for use and storage. This process also requires a potentially non-renewable feed stock (ethylene) typically a source of petroleum vapor cracking. SUMMARY
[008] In one embodiment, a reactive distillation method comprises introducing a feed stream to a reactive distillation column, contacting the feed stream with one or more catalysts in the reactive distillation column during a distillation, and removing one or more higher alcohols during the distillation of the reactive distillation column as a lower stream. The feed stream comprises one or more alpha hydrogen alcohols and the feed stream reacts in the presence of the one or more catalysts to produce a reaction product comprising the one or more higher alcohols. The feed stream may still comprise water. The one or more alpha hydrogen alcohols can comprise one or more of ethanol, propanol or butanol. The one or more alpha hydrogen alcohols can comprise only ethanol. The one or more higher alcohols can comprise a C4-C13 alcohol. The one or more higher alcohols may comprise at least one alcohol selected from the group consisting of: 1-butanol, 1-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-ethyl-2-hexanol, heptanol, decanol and dodecanols. The one or more catalysts may comprise a Guerbet reaction catalyst, a solid base multi-component oxide catalyst, a solid acid/base bifunctional catalyst, a zeolite with alkaline counterions, a magnesium oxide catalyst, an oxide powder catalyst , or any combination thereof. The one or more catalysts may comprise a dual-function catalyst. The one or more catalysts may comprise a hydroxyapatite Guebert reaction catalyst, a solid base Guebert reaction catalyst, or a combination thereof. The one or more catalysts may comprise CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2 CuO/Al2O3, CuO/MgO, CuO/MgO/SiO2, CuO/MgO/Al2O3, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/SiO2 and CuO/Na2O/SiO2, CuO/MgO/Al2O3/SiO2 CuO/CeO2/MgO/Al2O3, CuO/ZnO/Al2O3, CuO/Cr2O3/Al2O3 and CuO/ZrO2/Al2O3, or any combination thereof. The one or more catalysts can comprise copper and the copper can have a weight loading of between about 0.5% and about 80%. The one or more catalysts may comprise a catalyst component represented by the formula: M/MgO/Al2O3, where M may represent palladium, rhodium, platinum, silver, gold, nickel, or copper or oxides thereof. The one or more catalysts may comprise a hydroxyapatite represented by the formula: Ca10(PO4)6(OH)2, where the ratio of calcium to phosphorus (Ca:P) can be between about 1.5 and about 1.8. The one or more catalysts may comprise an apatite structure that satisfies the formula: Ma(M'Ob)CX2, where M represents calcium, strontium, magnesium, barium, lead, cadmium, iron, cobalt, nickel, zinc or hydrogen, where M' represents phosphorus, vanadium, arsenic, carbon or sulfur, where X represents a fluorine, chlorine, bromine or hydroxide and where a is about 10, b is about 3, c is about 6 and the ratio of aac is between about 1.5 and about 1.8. The one or more catalysts may comprise a calcium phosphate, a calcium carbonate phosphate, a calcium pyrophosphate, a magnesium phosphate, a magnesium carbonate phosphate, a magnesium pyrophosphate, magnesium oxide, magnesium hydroxide, magnesium phosphate hydrated (Mg3(POiH8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite ( Ca10(PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite, or any combination thereof. The one or more catalysts may comprise at least one catalyst component selected from the group consisting of: copper, barium oxide, barium, barium oxide, rethenium, ruthenium oxide, rhodium, rhodium oxide, platinum, platinum oxide, palladium, palladium oxide, rhenium, rhenium oxide, silver, silver oxide, cadmium, cadmium oxide, zinc, zinc oxide, z irconium, zirconium oxide, gold, gold oxide, thallium, thallium oxide, magnesium, magnesium oxide, manganese, manganese oxide, aluminum, aluminum oxide, chromium, chromium oxide, nickel, nickel oxide, iron, iron oxide, molybdenum, molybdenum oxide, sodium, sodium oxide, sodium carbonate, strontium, strontium oxide, thallium, thallium oxide and any mixture thereof. The one or more catalysts may comprise a multi-component catalyst and the catalyst multicomponent may comprise a first catalyst component and a second catalyst component. The first catalyst component can comprise a dehydrogenation catalyst component and the second catalyst component can be configured to convert at least a portion of the one or more alpha hydrogen alcohols in the feed stream into the reaction product comprising the one or more higher alcohols. and water. The one or more catalysts may comprise a support, and the support may comprise at least one support material selected from the group consisting of: carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride, nitride. boron, heteropolyacids, hydroxyapatite, zinc oxide, chromia, a zeolite, a carbon nanotube, carbon fullerene and any combination thereof. The reactive distillation method can also include: removing a side stream from the reactive distillation column; contacting the side stream with a secondary reactor catalyst, where the side stream reacts in the presence of the secondary reactor catalyst to produce at least one of the one or more higher alcohols and reintroduce the at least one of the one or more higher alcohols produced in the presence of the catalyst from the secondary reactor in the reactive distillation column. The side stream may comprise a steam, and contacting the side stream with the secondary reactor catalyst may comprise contacting the steam with the secondary reactor catalyst. The side stream may comprise a liquid and contacting the side stream with the secondary reactor catalyst may comprise contacting the liquid with the secondary reactor catalyst. The reactive distillation method can also include adjusting a sidestream flow rate to increase the production of the one or more higher alcohols.
[009] The reactive distillation method may also include: removing a plurality of side streams from the reactive distillation column, introducing each of the plurality of side streams into a corresponding plurality of side reactors, where each of the plurality of side reactors comprises at least at least one secondary reactor catalyst, contacting each of the plurality of side streams with the at least one secondary reactor catalyst in the corresponding plurality of side reactors, wherein each of the plurality of side streams reacts in the presence of the one or more secondary reactor catalyst to produce a higher alcohol and reintroduce the higher alcohol produced in the presence of the secondary reactor catalyst from each of the plurality of side reactors in the reactive distillation column. The reactive distillation method can also include adjusting a reactive distillation column pressure to increase the production of the one or more higher alcohols. The reactive distillation method can also include introducing a second feed stream comprising hydrogen into the reactive distillation column. The reactive distillation method can also include removing the bottom stream from the reactive distillation column, where the one or more upper alcohols comprise one or more C6-C13 alcohols and butanol, separating at least a portion of the one or more C6-C13 alcohols from one or more C2-C5 alcohols and recycle the one or more C2-C5 alcohols into the reactive distillation column.
[0010] In one embodiment, a reactive distillation system comprises a reactive distillation column comprising: a catalyst located generally centrally in the column, an ethanol feed in fluid communication with the reactive distillation column and configured to pass ethanol to ethanol over the catalyst, wherein the catalyst is configured to convert at least a portion of the ethanol feed to butanol in the reactive distillation column, a top product dewatering pass and a top product alcohol removal pass bottom; a product separation system comprising an inlet configured to receive bottom product from the reactive distillation column, an upper alcohol product removal passage and an ethanol removal passage, and a recycle line connecting the removal passage. ethanol from the product separation system and an inlet to the reactive distillation column. The reactive distillation column may comprise a continuous stirred tank reactor (CSTR) configured to contact a liquid ethanol feed with the catalyst and remove water during contact of the liquid ethanol feed with the catalyst.
[0011] In one embodiment, a method of separating a mixed aqueous and organic phase stream, the method comprises: separating an input stream into an upper stream and a lower stream into a separation unit, where the input stream comprises water, butanol and an ester, where the upper stream comprises water and the ester and where the lower stream comprises butanol, passing an upper stream to a decanter, generating, in the decanter, a phase comprising substantially all of the water and an organic phase comprising the esters, removing the aqueous phase from the decanter as an aqueous stream, removing the organic phase from the decanter as an organic stream, separating the organic stream into a product stream and a recycle stream, where the product stream comprises the esters and where the recycling stream comprises water. Esters can comprise one or more of ethyl butyrate, ethyl acetate and butyl acetate. The separation unit can comprise one or more distillation columns.
[0012] In one embodiment, a method of separating a mixed aqueous and organic phase stream comprises: separating an input stream into an upper stream and a lower stream into a separation unit, where the input stream comprises water, a plurality of higher alcohols and an ester, wherein the upper stream comprises the water the esters and a first portion of the plurality of higher alcohols and where the lower stream comprises a second portion of the plurality of higher alcohols, separating a lower stream into at least one product stream comprising a first higher alcohol from the first portion of the plurality of higher alcohols, passing an upper stream to a decanter, generating, in the decanter, a phase comprising substantially all of the water and an organic phase comprising the esters and the second portion of the plurality of higher alcohols, removing the aqueous phase from the decanter as an aqueous stream, removes r the organic phase from the decanter as an organic stream and separate the organic stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols. Separating a lower stream into at least one product stream may comprise: separating a lower stream into a first product stream comprising butanol and a second product stream comprising the remainder of the first portion of the plurality of higher alcohols. Separating a lower stream into at least one product stream may further comprise: separating the remainder of the first portion of the plurality of higher alcohols into a third product stream comprising hexanol. Separating the organic stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols may comprise: separating the organic stream into a second upper stream comprising the esters and water and a second lower stream comprising comprises the second portion of the plurality of higher alcohols. Separating the organic stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols may further comprise: passing the upper second stream to a second settler, generating, in the second settler, a second aqueous phase comprising substantially all of the water in the organic stream and a second organic phase comprising the esters, removing the second aqueous phase from the second decanter as a second aqueous stream, removing the second organic phase from the second decanter as a second stream of organics, separating the second stream of organics into a product stream of esters comprising the esters. Separating the organic stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols may further comprise: separating the lower second stream into a third upper stream and a third lower stream where the third stream higher comprises at least one higher alcohol from the second portion of the plurality of higher alcohols. Separating the second lower stream into a third upper stream and a third lower stream can occur at a pressure greater than about 3 atmospheres. Separating the organic stream into the first stream comprising the esters and the second stream comprising the second portion of the plurality of higher alcohols can take place in a distillation system and the distillation system can comprise a distillation column and at least one rectifier or extractor in fluid communication with a distillation column.
[0013] In one embodiment, a method of separating an alcohol from butyl acetate, the method comprises adding water to an input stream to form a combined stream, where the input stream comprises an alcohol and butyl esters, distilling the combined stream to produce an upper stream and a lower stream, where the upper stream comprises a water and ethyl acetate and where the lower stream comprises a majority of the alcohol, condense an upper stream and decant a phase comprising a stream from a stream of organic phase, where the aqueous phase stream comprises a majority of the water in an upper stream and where the organic phase stream comprises a majority of the butyl acetate in the upper stream.
[0014] These and other features will be more clearly understood from the following detailed description taken in conjunction with the drawings and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a more complete understanding of the present description and its advantages, reference is now made to the following brief description, made in connection with the accompanying drawings and detailed description.
[0016] Figures 1(a) and 1(b) show a simplified schematic of a reactive distillation system according to one embodiment.
[0017] Figure 2 shows a simplified scheme of a reactive distillation system according to yet another embodiment.
[0018] Figures 3(a) and 3(b) show a simplified scheme of a reactive distillation system according to yet another embodiment.
[0019] Figure 4 shows a simplified scheme of a reactive distillation system according to yet another embodiment.
[0020] Figures 5(a) and 5(b) show a simplified schematic of a reactive distillation system according to one embodiment.
[0021] Figures 6(a) and 6(b) show a simplified scheme of a reactive distillation system according to another embodiment.
[0022] Figures 7(a) and 7(b) illustrate a schematic flow diagram of a reactive distillation system with a recycle according to one embodiment.
[0023] Figure 8 illustrates a schematic flow diagram of a product separation system according to an embodiment.
[0024] Figure 9 illustrates a schematic flow diagram of a product separation system according to another embodiment. DETAILED DESCRIPTION
[0025] A reactive distillation system and process are described here for the production of higher linear and branched alcohols in a simple reactor or a reactive distillation process. As used herein, higher alcohols refer to alcohols that have a higher molecular weight than the alcohol that forms the reactant in the forming process. Higher alcohols can include n-butanol as well as significant amounts of 1-hexanol, 2-ethylbutanol, 1-octanol, 2-ethylhexanol and other higher alcohol isomers (eg, isomers of hexanol, octanol, etc.). This process is beneficial when it provides an improved commercial method of raising ethanol to higher alcohols such as n-butanol, which are more valuable products. This improved commercial process can be used when there is a supply and/or a supply and/or an excess supply of ethanol. In addition, this process reduces and/or eliminates the need for separate synthesis gas and n-butyraldehyde plants to provide the precursors for the production of butanol and reduces and/or eliminates the dependence on synthesis gas as a precursor, which is cheap. to be produced and requires a non-renewable resource when obtained from oil and natural gas. This process also reduces and/or eliminates the need for a separate acetaldehyde plant to supply the precursors for the butanol production process and reduces and/or eliminates dependence on highly toxic acetaldehyde.
[0026] The raw material of this process may comprise only ethanol, which may present an advantage over other processes that require multiple feed stocks. In addition, bio-derived ethanol can be used to allow the process to be operated from renewable ethanol sources. Furthermore, the present system and method can utilize metal-based catalysts, which can be less expensive than the precious metal-based catalyst from other butanol production routes and faster than microbial fermentation. Such catalysts can comprise copper and can be composed of barium oxide mixed with one or more additional metals and/or metal oxides. The present systems and methods can allow for a one-step butanol production process, which can be advantageous over other processes that require a complex arrangement of reactors and catalysts or a complex separation scheme. Each of these advantages can be provided in a process that can also be less expensive than alternative processes for producing butanol from ethanol.
[0027] Also described is a reactive distillation system and process for co-producing high purity higher alcohols and ethyl acetate from ethanol. This process is beneficial when it provides a commercial method of elevating ethanol to higher alcohols and/or ethyl acetate, which are more valuable products. The process can be adjusted to allow a relative proportion of each product to be controlled, thereby allowing for controlled product selection based on commercial considerations such as the cost of each product. Furthermore, this commercial process can be used when there is a supply and/or an excess supply of ethanol. as the process for producing higher alcohols such as butanol, this process reduces, and/or eliminates the need for a separate acetaldehyde, acetic acid, synthesis gas or n-butyraldehyde plant to provide the precursor for the process and reduces and/or eliminates dependence on synthesis gas and acetaldehyde precursors. While multiple alcohols can be used in feed, the raw material can comprise only ethanol, which can represent an advantage over other processes that require multiple feed stocks. In addition, bio-derived ethanol can be used to allow the process to be operated from renewable ethanol sources.
[0028] This process is still beneficial in that higher alcohols and/or ethyl acetate can be produced in a single step from the same process equipment. This single-step production can advantageously eliminate capital expenditures, operating costs and additional space requirements that would otherwise be required if the higher alcohols and ethyl acetate are to be produced separately. This single-step production can also advantageously avoid costly plant shutdowns that would otherwise be required to switch from one product to another in a process capable of producing only one product at a time. This process is also beneficial in that the relative amounts of higher alcohols and/or ethyl acetate can be adjusted during continuous operation to accommodate changes in market demand for one product relative to another. The present systems and methods may allow for a one-step process for producing higher alcohols and/or ethyl acetate, which may be advantageous over other processes that require additional steps for purification of the ethyl acetate product, including a removal selective 2-butanone, which forms a low-boiling azeotrope with ethyl acetate. each of these advantages can be provided in a process that can also be less expensive than alternative processes for producing ethyl acetate from ethanol.
[0029] In one embodiment, the reaction to manufacture higher alcohols from ethanol is believed to proceed via the Guerbet reaction mechanism. The initial step comprises a dehydrogenation of ethanol to form acetaldehyde. The acetaldehyde can then undergo an aldol condensation reaction to form an aldol intermediate which subsequently can be dehydrated to form crotonaldehyde. Crotonaldehyde can then be hydrogenated to butyraldehyde, which can further be hydrogenated to 1-butanol. Heavier alcohols can be generated in the same way, only butyraldehyde, crotonaldehyde or 1-hexanal participate in the aldol condensation reaction with acetaldehyde (or any other aldehyde present in the reaction mixture) resulting in 2-ethylalkyl alcohols (2-ethylbutanol, 2-ethylhexanol). A condensation of crotonaldehyde aldol intermediate with acetaldehyde and butyraldehyde is the pathway leading to 1-hexanol and 1-octanol respectively. Ethyl acetate can be produced by dehydration from dehydrogenation. These pathways are capable of producing high purity higher alcohols and/or ethyl acetate from alcohol feed streams (eg an ethanol feed stream) containing significant amounts of impurities. One goal in producing higher alcohols and/or ethyl acetate is that the reaction product mixture is commonly a complex mixture including esters, alcohols, aldehydes and ketones. From a separation point of view by distillation, mixing is still complicated due to the presence of azeotropes. The reaction product mixture may contain components with boiling points close to the higher alcohols produced which may include n-butanol (such as isobutanol), the hexanol, octanol and ethyl acetate isomers (such as n-butyraldehyde, butan-2 - one or a combination thereof), including components that can form azeotropes with one or more higher alcohol products, ethyl acetate, other components of the mixture or any combination thereof. This can avoid a challenge when one or more high purity higher alcohols and/or high purity ethyl acetate are desired.
[0030] In chemical processing, the chemical reaction and purification of the desired products by distillation can be carried out sequentially. The performance of this chemical process structure can be improved by integrating reaction and distillation into a single multifunctional process unit. This integration concept is called "reactive distillation." The reaction can take place within the same vessel or a second vessel in fluid communication with a separation vessel can be considered a reactive distillation. For example, a secondary reactor that carries a reaction that is in fluid communication with a distillation column that removes at least a portion of the products should be considered a reactive distillation process. As advantages of this integration, chemical equilibrium limitations can be overcome, higher selectivities can be achieved, heat of reaction can be used in situ for distillation, auxiliary solvents can be avoided, azeotropic and/or boiling mixtures roughly they can be more easily separated or any combination thereof. increased process efficiency and reduction in total capital costs can result from using this method.
[0031] A reactive distillation system comprises at least one separator (eg a distillation tower) in which a reaction is taking place. In general, suitable separators may include any process equipment suitable for separating at least one inlet stream from a plurality of effluent streams having different compositions, states, temperatures and/or pressures. For example, the separator can be a column having trays, packaging, or some other type of complex internal structure. Examples of such columns include scrapers, separators, absorbers, adsorbers, packed columns and distillation columns having valve, sieve or other types of trays. Such columns may comprise dikes, downspouts, internal baffles, temperature control elements, pressure control elements or any combination thereof. Such columns may also utilize some combination of reflux condensers and/or reheaters, including intermediate stage condensers and reheaters. In one embodiment, the reactive distillation system described herein may comprise a distillation tower having at least one catalyst disposed therein.
[0032] As indicated above, the present systems and methods provide for the production of higher alcohols from ethanol and/or for the production of higher alcohols and/or ethyl acetate at a relatively low cost together with distillation plants or systems with significantly reduced complexity using reactive distillation. The present description further provides improved processes for the production of one or more higher purity alcohols and for the production of higher purity alcohols and/or ethyl acetate from lighter alcohol feed or from a stock of feed comprising a greater proportion of the lighter alcohol feed and a lesser proportion of impurities such as iso-propanol, iso-butanol, water, or any combination thereof while not commonly present in alcohol feed streams, which impurities may contaminating the particular catalyst used must be limited, avoided and/or removed. For example, heterocyclic sulfur or nitrogen compounds can often act as catalyst contaminants and, if present, can be removed before introducing the alcohol feed stream into the reactive distillation column. In one embodiment, the alcohol feed can comprise water. The presence of water in the alcohol feed does not severely reduce the performance of catalysts, which can tolerate up to about 5% water by weight in the alcohol feed. Alcohol conversion is reduced when using an alcohol source with significant water content, but reaction selectivity may increase for some products. The use of an alcohol feed comprising a small amount of water may be advantageous in that it allows the use of a potentially less expensive source of alcohol in the form of the alcohol/water azeotrope (eg, about 4.4% water by weight in an ethanol feed). the effects of water are demonstrated in the Examples described herein.
[0033] Direct synthesis of higher alcohols from ethanol offers a potentially viable alternative to the hydroformylation process and ethylene oligomerization process described above. In the direct synthesis of higher alcohols from ethanol, ethanol, which is an easily available and renewable feedstock, is converted to a mixture of C4-C13 alcohols and potentially higher alcohols. In one embodiment, the ethanol feed stock can be converted to one or more of n-butanol, 1-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-ethyl-2-hexanol, decanols, potentially longer chain dodecanols and alcohols in a simple reactor or a reactive distillation mechanism in a solid catalyst. As noted above, the reaction to form higher alcohols from ethanol is generally believed to proceed via the Guerbet reaction mechanism.
[0034] As an example of a reaction mechanism for the production of a higher alcohol, butanol can be produced from ethanol in the presence of one or more catalysts according to the total dehydration reaction according to the following reaction of total dehydration: C2H5OH + C2H5OH C4H9OH + H2O (Eq. 1)
[0035] While not intending to be bound by theory, it is believed that the total reaction can proceed according to one or more of the following reactions in the presence of a catalyst: C2H5OH CH3CHO + H2 (Eq. 2) CH3CHO + CH3CHO CH3CH =CHCHO + H2O (Eq. 3) CH3CH=CHCHO + 2H2 C4H9OH (Eq. 4) C4H8O + H2 C4H9OH (Eq. 5)
[0036] The production of butanol and/or ethyl acetate from ethanol can be produced according to the following dehydration and dehydrogenation reactions that can occur in the presence of one or more catalysts: C2H5OH + C2H5OH C4H9OH + H2O (Eq. 1) C2H5OH CH3CHO + H2 (Eq. 2) CH3CHO + C2H5OH CH3COOC2H5 + H2 (Eq. 6)
[0037] In one embodiment, ethanol is reacted in a simple continuous reactive distillation column that provides sufficient residence time to tint a relatively high conversion of ethanol. In one embodiment, the reactive distillation column can be configured to provide an ethanol conversion of at least about 10% and a selectivity of at least about 60%, as described in more detail herein.
[0038] As noted above, higher alcohols refer to one or more alcohols having a higher molecular weight than the alcohol that forms the reactant in the forming process. For example, butanol should be considered a higher alcohol when produced from ethanol. As used herein, the term "butanol" may refer to n-butanol or mixtures of n-butanol in combination with 2-butanol, isobutanol, tert-butanol or a combination thereof unless specifically indicated otherwise. In various embodiments, butanol refers to n-butanol or mixtures of n-butanol in combination with 2-butanol, isobutanol, tert-butanol or a combination thereof, wherein n-butanol is the majority component in Weight. In addition to butanol, higher alcohols, in general, can comprise any C4-C13 alcohols or even higher molecular weight alcohols.
[0039] With respect to the alcohol that forms the reagent in the formation process, the present description is generally described in terms of ethanol. However, several alcohols can form the reagent. In some embodiments, the process is believed to occur with a feed comprising any alcohol that comprises an alpha hydrogen with respect to a hydroxyl group (e.g., an alpha hydrogen alcohol) that includes, but is not limited to, a primary alcohol. or secondary. In one embodiment, the feed may comprise one or more alcohols other than methanol and may include any alpha hydrogen C2-C5 alcohols. In addition, ethanol, additional alcohols can be used in feed which includes, but is not limited to, propanol, isopropanol, butanol, isobutanol, pentanol, etc.
[0040] The present systems and methods provide a reactive distillation system in which an alcohol feed comprising an alcohol having an alpha hydrogen is fed to a reactive distillation column. In one embodiment, ethanol can be the sole or primary component of the feed. Reference to a "single feed" to a reactive distillation column means that the column has only one chemical feed stream supplying desired reagents to the column. However, such a single distillation column can have multiple entry points for the reactant or recycle feed streams where a part of the reactant liquid or partial distillate is withdrawn from the column and fed back into the column at a different point, for example, to achieve improved separation and/or more complete reaction.
[0041] A simple feed may comprise a simple reagent such as alpha hydrogen alcohol (eg ethanol). A "simple alcohol feed" refers to a feed stream of a simple alpha hydrogen alcohol and a "simple ethanol feed" refers to a simple feed stream in which ethanol is the only or at least the constituent primary. The single feed may also comprise more than one reactant, such as an ethanol and water feed stream or a feed stream comprising a plurality of alpha hydrogen alcohols. A "simple ethanol and water feed", in this way, refers to a simple feed stream in which ethanol and water are the only or at least the primary constituents. In contrast, the term "dual feed" in the context of a distillation column refers to two separate chemical feed streams. For example, in some of the present embodiments, dual feeds can include an ethanol feed stream and a separate hydrogen feed stream. As another example, in some embodiments, dual feeds can include an ethanol and water feed stream and a separate hydrogen feed stream. similarly, the term "triple feed" in the context of a distillation column refers to three separate chemical feed streams. For example, in some of the present embodiments, three feeds are an ethanol feed stream (or, alternatively, an ethanol and water feed stream), a separate water feed stream, and a separate hydrogen feed stream. . As another example, in some of the present embodiments, three feeds may include an ethanol feed stream, a propanol feed stream, and a separate hydrogen feed stream.
[0042] The term "reactive distillation column" is used conventionally to refer to a distillation column in which e separation is carried out while a reaction is taking place. The reaction can take place within the same distillation column or a second vessel in fluid communication with a distillation column can still be considered a reactive distillation column. For example, a secondary reactor that carries a reaction that is in fluid communication with a distillation column that removes at least a portion of the products should be considered as a reactive distillation process that takes place in a reactive distillation column.
[0043] In general, higher alcohols are produced by adding one or more lighter alcohols and/or by-products. In embodiments where production of butanol is desired, the primary and desired reaction is the conversion of two molecules of ethanol and one molecule of butanol with the release of one molecule of water. To this end, the present application provides systems and methods for producing higher alcohols from an alpha hydrogen alcohol, such as ethanol, which include reacting one or more alpha hydrogen alcohols in a suitable catalyst in a reactive distillation column, such way, producing higher alcohols and water. In embodiments where the production of higher alcohols and/or ethyl acetate is desired, the primary and desired reactions include the conversion of two alpha hydrogen molecules to a higher alcohol molecule with the release of a water molecule and conversion from two ethanol molecules to one ethyl acetate molecule with the release of two hydrogen molecules. To this end, the present application provides systems and methods for producing higher alcohols and/or ethyl acetate from an alpha hydrogen alcohol, which includes reacting one or more alpha hydrogen alcohols in a suitable catalyst in the reactive distillation column, thereby producing one or more higher alcohols, ethyl acetate, water and any combination thereof. In some embodiments, by-products can also be produced as described in more detail herein.
[0044] In one embodiment, a simple reactive distillation column is used. Water is removed (eg, continuously) from the top of the reactive distillation column as an overhead stream. In some embodiments, the upper stream may comprise some amount of the alpha hydrogen alcohols present in the feed, such as ethanol. Higher alcohols can be removed (eg continuously) from the bottom of the column as a lower stream. Optionally, contamination by-products present following the reaction of the alpha hydrogen alcohols on the conversion catalyst can be reacted in a suitable hydrogenation catalyst at the bottom of the column or in a separate hydrogenation reactor. Hydrogenation can hardly convert to separate the by-products into species which are easier to separate from the higher alcohols. Consequently, the process can also include purification of the higher alcohols, including separating one or more higher alcohols, by distillation which results in hydrogenated by-products.
[0045] In some embodiments, a simple reactive distillation column is used for the co-production of higher alcohols and ethyl acetate. hydrogen gas and liquid water are removed (eg, continuously) from the top of the reactive distillation column as overhead streams. Higher alcohols and ethyl acetate are removed (eg, continuously) from the bottom of the column as a lower product stream. After leaving the reactive distillation column, the lower product stream can be subjected to further separation to isolate the higher alcohols from ethyl acetate, thereby producing the high purity product streams from each. Optionally, contamination by-products present following the reaction of the alpha hydrogen alcohols in the conversion catalysts can be reacted in a suitable hydrogenation catalyst at the bottom of the column or in a separate hydrogenation reactor. Hydrogenation can hardly convert to separate the by-products into species that are easier to separate from the higher alcohols, ethyl acetate or a combination thereof. Consequently, the process can also include purification of the higher alcohols and ethyl acetate products by separation (eg distillation) resulting in hydrogenated by-products.
[0046] In one embodiment, the reactive distillation column is configured by dehydrating an alpha hydrogen alcohol (eg ethanol) with the formation of a higher alcohol (eg butanol). The reaction is carried out by passing the alpha hydrogen alcohol feed stream over a suitable catalyst under the conditions where the higher alcohols are formed, water and any unreacted alpha hydrogen alcohols are withdrawn as top products and the higher alcohols can be withdrawn as an inferior product. Such product withdrawal drives the thermodynamics of the process with respect to the desired products. In this simplest form, a reactive distillation system can comprise a reactor vessel that operates with a liquid phase reaction in which water and any alpha hydrogen alcohols are removed as the upper product and a reaction product is removed as the lower product . The reactor vessel may comprise a continuous stirred tank reactor (CSTR). Alternatively, such a system may comprise a batch reactor in which water and any unreacted alpha hydrogen alcohols are removed during the reaction and the liquid product is removed after completion of the reaction to a desired degree of conversion.
[0047] In one embodiment, the reactive distillation column is configured for the dehydration of an alpha hydrogen alcohol (for example, ethanol) with the formation of higher alcohols (for example, butanol) and the dehydrogenation of the alpha hydrogen alcohol ( for example, ethanol) with the formation of ethyl acetate. reactions can be carried out by contacting a hydrogen feed stream with one or more suitable catalysts (eg a dehydration and dehydrogenation catalyst) under conditions where higher alcohols and ethyl acetate are formed, water and hydrogen are withdrawn as products top and the higher alcohols and ethyl acetate are withdrawn as lower products. By withdrawing the products from the distillation column, the thermodynamics of the process can be conducted with respect to the desired products. In its simplest form, a reactive distillation system can comprise a reactor vessel that operates with a liquid phase reaction in which water and/or other light gases are removed as a superior product and a reaction product is removed as the product. bottom. Such a system may comprise a batch reactor in which water is removed during the reaction and liquid product is removed after completion of the reaction to a desired degree of conversion.
[0048] In a simplistic way, as shown in Figure 1(a), the reactive distillation system can comprise a continuous stirred tank reactor (CSTR) loaded with a catalyst that is connected to a phase separator and configured for dehydration of an alpha hydrogen alcohol with the formation of one or more higher alcohols, the dehydration and dehydrogenation of the alpha hydrogen alcohol with the formation of one or more higher alcohols, and ethyl acetate (eg, the production of higher alcohols and/or acetate of ethyl) or a combination thereof. In one embodiment, the production of higher alcohols can be accomplished by passing the feed stream 14, which comprises a feed of an alpha hydrogen alcohol or an alpha hydrogen alcohol and water, into the CSTR 23 where the feed mixes and contacts the hydrogenation catalyst under the conditions where higher alcohols and water are formed. When the conversions proceeded, the resulting mixture may pass to a 32 stage separator from which water leaves as distillate 34 and higher alcohols including any butanol or heavier alcohols may leave as a lower product 36. The 32 stage separator may be any phase separator, which is a vessel that separates an incoming stream into a stream substantially of vapor and a stream substantially liquid, such as a knockout drum, scintillating drum, reheater, condenser, or other heat exchanger. Such containers may also have some internal baffles, temperature control elements, pressure control elements or any combination thereof, but in general they miss any trays or other complex internal structure commonly found in columns. In another embodiment, the production of higher alcohols and/or ethyl acetate can be carried out by passing a feed stream 14, which comprises a feed of one or more alpha hydrogen alcohols or one or more alpha hydrogen alcohols and water and, optionally, a hydrogen feed stream 21 into the CSTR 23 wherein the alpha hydrogen alcohols and any water and/or hydrogen mix and contact the conversion catalyst under conditions where one or more higher alcohols, ethyl acetate, water and hydrogen are formed. when the conversion proceeds, the resulting mixture can pass to a phase separator 32 where hydrogen, water and any unreacted alpha hydrogen alcohols are removed as the upper product stream 34 while the higher alcohols and ethyl acetate are removed as a stream of inferior product 36.
[0049] An embodiment of the reactive distillation column with a simple alpha hydrogen feed, eg a simple ethanol feed, is shown schematically in Figure 1(b). Column 10 contains a generally central catalyst zone 12 and will usually include an upper stage or non-reactive rectifying section 13 and a lower stage or non-reactive withdrawal section 15. The alpha hydrogen alcohol feed 14 may be fed separately average of the reactive distillation column. While illustrated as having catalyst 17 disposed within the central portion of column 10, catalyst 17 may be located just above or below the alpha hydrogen alcohol feed site. In one embodiment, catalyst 17 may be disposed just above the feed location and the lower portion of column 10 may comprise trays, packaging or the like to provide a take-out section. In some embodiments, catalyst 17 may be disposed just below the feed location and the upper portion of column 10 may comprise trays, packaging or the like to provide a grinding section.
[0050] The distillate removed at the top of the column is passed through a partial condenser 16 and the water is separated from the lower boiling constituents in a reflux tank 18. The higher boiling constituents can leave the system as an upper product stream 19, which in one embodiment may comprise trace amounts of water, the alpha hydrogen alcohols in the feed (eg ethanol), higher alcohols (eg butanol, 2-butanol, isobutanol, etc.), one or more by-products reaction, or any combination thereof. The condensate (eg, reflux) or at least some portion of it, can be circulated back to the column for further reaction and/or separation. The condensate is not circulated back to the column as the upper product stream 11. The condensate comprises water and, in some embodiments, the alpha hydrogen alcohols from the feed. The condensate may also comprise trace amounts of additional components including alpha hydrogen feed alcohols, higher alcohols, one or more reaction by-products, or any combination thereof. In one embodiment, a portion of the condensate comprising water and the alpha hydrogen alcohol may be dehydrated and returned to the column 10. The bottom product can be passed through the reheater 20, where a portion of the bottom product is converted to steam and introduced back to the bottom portion of the column. The remaining bottom product can pass from the system as product stream 22. Alternatively, only a portion of the bottom product can be passed through the reheater 20, with the steam portion passing back to the bottom portion of the column and the remainder of the bottom product being combined with any inferior product that bypasses reheater 20 and passes from the system as product stream 22 for further processing and/or use as an end product. Product stream 22 can comprise the higher alcohols produced in the column potentially together with side products produced by the reaction. Some trace amounts of the alpha hydrogen alcohols feed may be present in the lower stream 22. In one embodiment, the lower stream may comprise butanols, pentanols, any C6-C13 alcohols, heavier alcohols, or any combination thereof. Column reflux and reheat ratios can be maintained such that one or more essentially pure higher alcohols can be obtained as the lower product. In one embodiment, the lower product stream 22 can comprise more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% higher alcohols by weight. In some embodiments, lower product stream 22 can comprise more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99% or more than about 99.5% butanol by weight.
[0051] During operation, reactants and products flow through the reactor/column which reacts and scintillating along the length of the reactor/column. In one embodiment, the reaction of reactants and/or products can take place in catalyst zone 12 and reactions can take place in the vapor and/or liquid phase. The specific catalysts useful in the reactive distillation system and methods described here are discussed in more detail below. In one embodiment, the alpha hydrogen alcohol reaction over catalysts can occur in a vapor phase in which ethanol is passed over the catalyst for a given residence time consistent with the desired selectivity and/or conversion. In one embodiment, the reaction of ethanol on catalysts can take place in a liquid phase reaction where the catalyst can be dispersed in a liquid reactant mixture and/or the reactants contact the catalyst in a condensed state. A vapor phase reaction and a liquid phase reaction, in general, should generally take place at similar temperatures and the pressure of each reaction should depend on the state (eg, vapor and/or liquid) of the reactants contacting the catalysts.
[0052] One or more higher alcohols and water can be produced, along with potential by-products, due to the reaction on the catalyst. Removal of the upper current removal 11 comprising water, which can occur by scintillation, increases the extent of reaction. In general, the water concentration increases from the middle part of the column towards the top of the column. A partial condenser 16 allows water to be removed as a distillate and/or recycled back to the top of the reactive distillation column. At pressures of about 0.1 bar or greater, an azeotrope occurs between ethanol and water while ethanol is present in the alpha hydrogen alcohol feed that is introduced with the feed and/or formed from the reactant. This azeotrope can result in the top product 11 which leaves the top of the reactive distillation column 10 containing unreactive ethanol in addition to water. In one embodiment, any unreacted ethanol that leaves condenser 16 as upper stream 11 can be fed to a dehydration unit to produce a stream of dehydrated ethanol, which can then be recycled back to column 10 as the feed.
Column 10 can be operated at any suitable pressure between about 1 atm and about 80 atm. In one embodiment, column 10 can be operated at a pressure ranging from about 1 atm to about 5 atm, about 5 atm to about 10 atm, about 10 atm to about 20 atm, about 15 atm to about 20 atm, about 15 atm to about 30 atm, about 20 atm to about 30 atm, about 20 atm to about 50 atm, about 30 atm to about 40 atm, about 40 atm to about 50 atm or about 50 atm to about 60 atm, about 60 atm to about 70 atm, about 60 atm to about 80 atm, or about 70 atm to about 80 atm. The temperature profile in a column is dictated by the boiling point of the mixture over the height of the column. In one embodiment, the temperature inside the column can range from about 100°C to about 400°C, about 150°C to about 350°C, about 200°C to about 325°C, about 230°C to about 300°C, or about 260°C to about 300°C. Column 10 can comprise any number of stages equivalent to several theoretical stages sufficient to carry out the reaction and separation of alcohols greater than a desired purity. In one embodiment, the number of stages or the number of height equivalents of a theoretical plate (HETP) can range from about 1 to about 100, including, for example, from about 1 to about 10, about 10 to about 20, about 10 to about 50, about 20 to about 30, about 20 to about 70, about 30 to about 40, about 30 to about 50, about 30 to about 100, about 50 to about 70, about 50 to about 100, or about 70 to about 100. As described in more detail below, a relatively high conversion of alpha hydrogen alcohols to products can be achieved by counter-current flow of reactants and products in addition to overcoming the reaction equilibrium by removing the products through concurrent distillation within column 10.
[0054] In a reactive distillation process for the manufacture of higher alcohols, the maximum temperature of the catalyst in a column can be controlled by adjusting the operating pressure of the column. By increasing the pressure and therefore the temperature, a larger field of higher alcohols can be realized. The distribution and product can also be pulsed towards higher molecular weight higher alcohols as the temperature increases. Similarly, by decreasing operating pressure and therefore temperature, the process can be adjusted to make less higher alcohols along with the product distribution being pushed towards higher alcohols of lower molecular weight. Also, by selectively locating the catalyst section within column 10, a temperature within the catalytic section can be controlled, thereby controlling product distribution.
[0055] An alternative process for making higher alcohols directly from alpha hydrogen alcohols such as ethanol in a reactive distillation column with a single catalyst is to use the multiple catalysts in a simple process. In a reactive distillation column, the reactive sections can include both a catalyst for a first product production (eg, ethyl acetate, butanol, etc.) and a catalyst for the production of higher alcohols. The catalysts in each section can be configured to react at a temperature in the portion of the column where the catalysts are located.
[0056] In one embodiment, the system of Figure 1(b) can be used to co-produce butanol and ethyl acetate. In general, the process described above with respect to producing one or more higher alcohols from a feed comprising one or more alpha hydrogen alcohols will be the same or similar when co-production of higher alcohols and ethyl acetate is desired. As a result, similar elements will not be described here in the interest of brevity. The production of ethyl acetate together with higher alcohols can produce hydrogen as a reaction product. The distillate removed at the top of the column is passed through a partial condenser 16 and the hydrogen is separated from the higher boiling constituents in a reflux tank 18. The hydrogen can leave the system as an upper product stream 19, which in a form of embodiment may comprise trace amounts of additional components including alpha hydrogen alcohol from a feed stream, ethyl acetate, one or more higher alcohols, water, one or more reaction by-products, or any combination thereof. be passed through reheater 20, where a portion of the lower product is evaporated and added back to the lower portion of the column. Product stream 22 can comprise the higher alcohols and ethyl acetate produced in the column and potentially any portion of any by-products produced by the reaction. Column reflux and reheat ratios can be maintained such that the lower product is essentially all higher alcohols and ethyl acetate. In one embodiment, the lower product stream 22 can comprise a combined amount of higher alcohols and ethyl acetate that accounts for more than about 90%, more than about 95%, more than about 96% , more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% of the total weight of the product stream 22.
[0057] In one embodiment, the ratio of higher alcohols to ethyl acetate in the product stream 22 can be realized by the catalyst used as well as the amount of water and/or hydrogen introduced into column 10. With respect to reagents, the Ratio of higher alcohols to ethyl acetate can be adjusted by adjusting an amount of water and/or hydrogen fed to column 10. An amount of water can be introduced with the alpha hydrogen alcohol feed as part of the feed stream 14. of hydrogen can be introduced with alpha hydrogen alcohol, separately as feed stream 21 or a combination thereof. To increase an amount of higher alcohols produced relative to the amount of ethyl acetate produced, the amount of water introduced into a feed stream 14 can be increased and/or the amount of hydrogen introduced into column 10 in a feed stream 21 can be diminished. To increase an amount of ethyl acetate produced relative to the amount of higher alcohols produced, the amount of hydrogen introduced into column 10 in a feed stream 21 can be increased and/or the amount of water introduced into a feed stream 14 can be diminished.
[0058] In one embodiment, the systems and methods may also include hydrogenation contaminants or reaction by-products in the lower stream or in the reacted fluid after it has passed over the upper alcohol conversion catalyst and separate the hydrogenated contaminants or by-products from the higher alcohols. Species that can be produced as by-products in the reaction can include aldehydes, such as acetaldehyde, n-butyraldehyde and/or crotonaldehyde; ethers such as ethyl ether and n-butyl ether; ethyl acetate. Various higher alcohols can also be produced including, but not limited to, isobutanol, 2-butanol, 2-ethylbutanol, n-hexanol, 2-ethylhexanol, 2-ethylbutanol, 1-octanol, other hexanol isomers, and/or other octanol isomers and/or various higher alcohols and isomers thereof. Some of these by-products boil at temperatures close to the boiling point of one or more desired higher alcohols and can be difficult to separate.
[0059] Figure 2 shows a schematic process where the bottom product 22 of the reactive distillation column 10 illustrated in Figure 1(b) is sent to a hydrogenation reactor 24 comprising a hydrogenation catalyst 26 with a hydrogen co-feed 28. Suitable hydrogenation catalysts can comprise various components and are described in more detail herein. At least a portion of the by-products can be hydrogenated, passed through heat exchanger 30 and can then be separated using a separator 32. Separator 32 can comprise any of the types of separators described herein with respect to the reactive distillation system. Alternatively or in addition to the separators already described, the separator 32 may be a phase separator, which is a container that separates an incoming stream substantially into a stream of vapor and substantially a stream of liquid, such as a knockout drum, flash drum , reheater, condenser or other heat exchanger. Such containers may also have some internal baffles, temperature control elements, pressure control elements, or any combination thereof, but in general they need any trays or other type of complex internal structure commonly found in columns. The separator can also be any other type of separator, such as a membrane separator. In a specific embodiment, the separator is a knockout drum. Finally, the separator can be any combination of the aforementioned separators arranged in series, in parallel or combinations thereof. In one embodiment, separator 32 comprises a distillation column. The output of the hydrogenation reactor 24 can be passed through a heat exchanger 30 (eg a condenser) and cooled before entering the separator 32. The heat exchanger 30 can be any equipment suitable for heating or cooling a stream using up another chain. In general, heat exchanger 30 is a relatively simple device that allows heat to be exchanged between the two fluids without directly contacting each other. Examples of suitable heat exchangers 30 include, but are not limited to, shell and tube heat exchangers, twin tube heat exchangers, flat fin heat exchangers, bayonet heat exchangers, reheaters, condensers, evaporators and coolers of air. In the case of air coolers, one of the fluids comprises atmospheric air, which can be forced into tubes or spirals using one or more fans.
Lower product stream 36 from separator 32 may comprise one or more higher alcohols (e.g., butanols, pentanols, etc.) and may have a purity of greater than about 90%, greater than about 95 %, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% by weight. Unconverted water and hydrogenated by-products can be removed as a superior product 34 and can be used, for example, as fuel or a feed to one or more processes. In one embodiment, the separator 32 is operable between a pressure of 1 atm and 80 atm.
[0061] In one embodiment, the lower product stream 36 may pass to another separator. The separator can then separate the lower product stream into a stream of higher alcohols and a stream by-product comprising one or more heavier hydrogenation products produced in hydrogenation reactor 26. The components within a stream of mixed higher alcohols can still be separated to produce one or more product streams comprising predominantly individual higher alcohols. This separation scheme can allow one or more resulting higher alcohol streams to have individual component purities of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% of the respective higher alcohol by weight. In one embodiment, the product stream and may have a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than that about 98%, more than about 99%, or more than about 99.5% n-butanol by weight.
[0062] In one embodiment, the system of Figure 2 can also be used to co-produce one or more higher alcohols and ethyl acetate. In general, the process described above with respect to producing one or more higher alcohols from a feed comprising one or more alpha hydrogen alcohols in Figure 2 will be the same or similar when co-production of higher alcohols and ethyl acetate is desired. . As a result, similar elements will now be described with reference to Figure 2 in the interest of brevity. Figure 2 shows a schematic process where bottom product 22 from reactive distillation column 10 illustrated in Figure 1(b) is sent to a hydrogenation reactor 24 which comprises a hydrogenation catalyst 26 with a hydrogen co-feed 28. Suitable hydrogenation may comprise various components and are described in more detail herein. At least a portion of the by-products can be hydrogenated and then can be separated using a separator 32. The separator 32 can comprise any of the types of separators described herein with respect to the reactive distillation system, including those discussed above with respect to the separator 32. In one embodiment, separator 32 comprises a distillation column. The output of the hydrogenation reactor 24 can be passed through a heat exchanger 30 (eg a condenser) and cooled before entering the separator 32. The heat exchanger 30 can be any equipment suitable for heating or cooling a stream using another stream is available and can include any of those types of heat exchangers discussed here.
[0063] Lower product stream 36 from separator 32 may comprise one or more higher alcohols and ethyl acetate. The combined weight of the higher alcohols and ethyl acetate can comprise more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99% or more than about 99.5% of the total weight of the lower product stream. Water, hydrogen and unconverted hydrogenated by-products can be removed as a superior product 34 and can be used, for example, as fuel or a feed to one or more processes. In one embodiment, the separator 32 is operable between a pressure of 1 atm and 80 atm.
[0064] In one embodiment, the lower product stream 36 may pass to another separator. The separator can then separate the lower product stream into a stream comprising one or more higher alcohols and ethyl acetate and a byproduct stream comprising one or more heavier hydrogenation products produced in hydrogenation reactor 26. This separation scheme can allow the resulting stream of higher alcohols and ethyl acetate to comprise more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99% or more than about 99.5% of the total weight of the higher alcohols and ethyl acetate stream.
[0065] In one embodiment, the stream comprising the one or more higher alcohols and ethyl acetate may pass to another separator. The separator can then separate the butanol and ethyl acetate stream into an ethyl acetate upper stream and a lower stream comprising predominantly the one or more higher alcohols. This separation scheme can allow the resulting ethyl acetate upper stream to have a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97% , more than about 98%, more than about 99%, or more than about 99.5% ethyl acetate by weight. This separation scheme can allow the resulting lower stream comprising the one or more higher alcohols to have a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% higher alcohols by weight. In one embodiment, the resulting understream may comprise butanol having a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% butanol by weight.
[0066] In another embodiment of the invention, the reactive distillation column has two feeds. A schematic for the double feed reactive distillation column is schematically illustrated in Figure 3(a). The feed stream comprising the alpha hydrogen alcohol feed can be fed to the top of the column (top feed stream 46) and the hydrogen can be fed to the bottom of the column (bottom feed stream 48). This system includes column 40 containing catalyst 42 in catalyst zone 44 and may commonly include an upper stage or non-reactive rectifier section 50 and a lower stage or non-reactive withdrawal section 52. In the illustrated system, the upper feed stream 46 is released at or near the top of the catalyst zone 44 and the lower feed stream 48 is released at or near the bottom of the catalyst zone 44. In one embodiment, the upper feed stream 46 comprises at least one alpha hydrogen alcohol and water. It should be recognized that columns can be designed with the upper feed stream 46 at other locations, for example, within the catalyst zone 44 but above the lower feed stream 48, such as from the approximate half of the catalyst zone 44 at the top of column 40. Similarly, columns with lower feed stream 48 at other locations may also be designed, for example, with lower feed stream 48 from the approximate half of catalyst zone 44 to the bottom of column 40 or even higher within the catalyst zone 44 but below the upper feed stream 46. In one embodiment, the upper feed stream 46 and the lower feed stream 48 are sufficiently separated to allow hydrogenation of the by-product to be substantially completed before the hydrogen from the bottom feed reaches substantial concentrations of the alpha hydrogen alcohol being dehydro begotten. Alpha hydrogen alcohol (eg ethanol) reacts on the catalyst producing one or more higher alcohols and water. Examples of suitable conversion catalysts for use in the production of one or more higher alcohols are described in more detail herein.
[0067] Due to differences in boiling point, water tends to move towards the top of column 40 and higher alcohols tend to move towards the bottom of column 40. By-products such as acetaldehyde , n-butyraldehyde and ethyl ether can be produced during the reaction and can move through column 40. At least a portion of the by-products, if present, can be condensed in a condenser 54 (eg, a partial condenser or a full condenser ), passed through reflux tank 56 and recycled back to column 40 as reflux. Product stream 47 comprising water is withdrawn as distillate from reflux tank 56. In one embodiment, product stream 47 may further comprise unreacted alpha hydrogen alcohols from the feed and may contain a portion of by-products (per example, acetaldehyde, n-butyraldehyde, ethyl ether, crotonaldehyde, etc.). The product stream 47 comprising the alpha hydrogen alcohol and water can be fed to a dehydration unit to produce a dehydrated alpha hydrogen alcohol stream, which can then be recycled back to column 40 as feed. A portion of the lower withdrawal is withdrawn as the higher alcohols product stream 58, while the remaining portion is passed through reheater 60 to be recycled to a column 40. In one embodiment, the lower withdrawal may be passed through a reheater (e.g., similar to reheater 60) and optionally passed to a separator where the portion of steam can be passed to a column 40 while at least a portion of the remainder is withdrawn as higher alcohol product streams 58. through reheater 60 provides the effect of evaporation and vapor flow for the operation of column 40. In one embodiment, product stream 58 may comprise the higher alcohols in a column 40 and potentially any by-products by the reaction.
[0068] By-products such as ethyl acetate and n-butyraldehyde produced in the reaction may have boiling points close to the boiling point of one or more higher alcohols such as butanol. The lower hydrogen feed 48 is useful in hydrogenating the by-products to produce components that can be more easily separated from the higher alcohol products. The feed ratio of the alpha hydrogen alcohols to the feed can be beneficially adjusted to minimize the amount of near-boiling by-products. In one embodiment, the molar ratio of alpha hydrogen alcohols to hydrogen ranges from about 1:10 to about 1000:1, for example, from about 1:10 to about 1:1, from about 1: 1 to about 5:1, from about 1:1 to about 10:1, from about 5:1 to about 25:1, from about 5:1 to about 50:1, from about 10:1 to about 50:1, from about 10:1 to about 100:1, from about 50:1 to about 200:1, from about 50:1 to about 400:1, of from about 100:1 to about 500:1, from about 100:1 to about 1000:1, from about 200:1 to about 1000:1 or from about 500:1 to about 1000:1 . The aqueous product of the reaction leaves the top of the column. In one embodiment, column 40 may operate under any of the conditions (e.g., operating pressure, operating temperature, etc.) discussed herein with respect to column 10 in Figure 1(b). Furthermore, column 40 may have any number of stages and, in one embodiment, have any number of stages as described with respect to column 10 in Figure 1(b).
[0069] In another embodiment of the invention, the reactive distillation column comprises three feeds. A schematic for the reactive triple feed distillation column is schematically illustrated in Figure 3(b). A feed 46 comprising at least one alpha hydrogen alcohol can be fed to the top of the column (upper feed stream), a feed stream 48 comprising hydrogen can be fed to the bottom of the column (lower feed stream) and a intermediate feed stream 49 can be fed to a part of the column between the upper and lower parts of the column. In one embodiment, the intermediate feed stream 49 may comprise water. This system includes column 40 containing catalyst 42 in catalyst zone 44, and commonly may include an upper stage or non-reactive grinding section 50 and a lower stage or non-reactive withdrawal section 52. In the illustrated system, the stream of Upper feed 46 is released at or near the top of catalyst zone 44, lower feed stream 48 is released at or near the bottom of catalyst zone 44, and a feed stream 49 is released at or near half of the catalyst zone, between upper feed stream 46 and lower feed stream 48. In one embodiment, intermediate feed stream 49 comprises an alpha hydrogen alcohol and water. In some embodiments, the intermediate feed stream 49 may comprise an alpha hydrogen alcohol, which may be the same or different as the alpha hydrogen alcohol in the upper feed stream 46. It should be recognized that columns can be designed with the alpha hydrogen alcohol feed stream 46 at other locations, for example, within catalyst zone 44 but above lower feed stream 48 and intermediate feed stream 49, such as from the approximate half of catalyst zone 44 to the top of column 40. Similarly, the columns with the lower feed stream 48 at other locations, for example, within the catalyst zone 44 but below the intermediate feed stream 49 and the upper feed stream 46, such as the approximate half of the zone. from catalyst 44 to the bottom of column 40. Columns with intermediate feed stream 49 at other locations can also be designed, for example, with the intermediate feed stream 49 from approximately half of the catalyst zone 44 to the bottom of the column 40 but above the lower feed stream 48 or even higher within the catalyst zone 44 but below the upper feed stream 46. In one way of embodiment, the upper feed stream 46, the lower feed stream 48 and the intermediate feed stream 49 are sufficiently separated to allow the hydrogenation of the by-product to be substantially completed before the alpha hydrogen alcohol and optionally water or a combination of the two. even from the upper feed stream, the intermediate feed stream or a combination thereof achieves substantial concentrations of hydrogen. Alpha hydrogen alcohol fed to a column reacts on the catalyst to produce one or more higher alcohols, ethyl acetate, water and hydrogen. Examples of suitable hydration, dehydrogenation and dimerization catalysts are described in more detail herein.
[0070] Due to the boiling point differences, water and hydrogen tend to move towards the top of column 40 while the higher alcohols and any ethyl acetate tend to move towards the bottom of column 40. By-products , such as acetaldehyde, n-butyraldehyde, and ethyl ether can be produced during the reaction and can move through column 40. At least a portion of the by-products, if present, can be condensed in a condenser 54 (eg, a partial condenser or a full condenser), passed through reflux tank 56 and recycled back to column 40 as reflux. Product stream 59 comprising hydrogen is withdrawn from reflux tank 56. In one embodiment, product stream 59 further comprises ethyl ether. Product stream 47 comprising water may be withdrawn from reflux tank 56. In one embodiment, product stream 47 may further comprise unreacted alpha hydrogen alcohol. The product stream 47 comprising the alpha hydrogen alcohol and water can be fed to a dehydration unit to produce an alpha hydrogen alcohol stream, which can then be recycled back to column 40 as feed (e.g., as part of the top supply 46 and/or intermediate supply current 49). A portion of the withdrawn bottom is withdrawn with a product stream of one or more higher alcohols and ethyl acetate 58, while the remaining portion is passed through reheater 60 to be recycled to a column 40. In one embodiment, the portion The withdrawn bottom can be passed through a reheater (e.g. similar to reheater 60) and optionally passed to a separator where the portion of steam can pass to a column 40 while at least a portion of the remainder is withdrawn as a product stream from the one or more higher alcohols and ethyl acetate 58. The stream passing through reheater 60 provides the evaporation effect and vapor flow to operate column 40. Product stream 58 can comprise the one or more higher alcohols and acetate of ethyl produced in a column along with unreacted alpha hydrogen alcohols and potentially any by-products produced by the reaction.
[0071] By-products such as n-butyraldehyde and butan-2-one produced in the reaction may have boiling points close to the boiling points of one or more of the higher alcohols and ethyl acetate. The lower hydrogen feed stream 48 is useful in hydrogenating the by-products to produce components that can be separated from the higher alcohols. The feed ratio of the alpha hydrogen alcohols to the water feed, the feed ratio of the alpha hydrogen alcohols to the hydrogen feed, or a combination thereof, can be beneficially adjusted to minimize the amount of near-boiling by-products while not reducing excessively producing higher alcohols, ethyl acetate or a combination thereof In one embodiment, the molar ratio of alpha hydrogen alcohols to water ranges from about 1:10 to about 1000:1, eg, from about 1:10 to about 1:1, from about 1:1 to about 5:1, from about 1:1 to about 10:1, from about 5:1 to about 25:1, from from about 5:1 to about 50:1, from about 10:1 to about 50:1, from about 10:1 to about 100:1, from about 50:1 to about 200:1 , from about 50:1 to about 400:1, from about 100:1 to about 500:1, from about 100:1 to about 1000:1, from about 200:1 to about 1000 :1 or from about 500:1 to about 1000:1. In one embodiment, the molar ratio of alpha hydrogen alcohols to hydrogen ranges from about 1:10 to about 1000:1, for example, from about 1:10 to about 1:1, from about 1: 1 to about 5:1, from about 1:1 to about 10:1, from about 5:1 to about 25:1, from about 5:1 to about 50:1, from about 10:1 to about 50:1, from about 10:1 to about 100:1, from about 50:1 to about 200:1, from about 50:1 to about 400:1, of from about 100:1 to about 500:1, from about 100:1 to about 1000:1, from about 200:1 to about 1000:1 or from about 500:1 to about 1000:1 . In one embodiment, column 40 may operate under any of the conditions (e.g., operating pressure, operating temperature, etc.) discussed herein with respect to column 10 in Figure 1(b). Furthermore, column 40 may have any number of stages and in one embodiment have any number of stages as described with respect to column 10 in Figure 1(b).
[0072] As schematically illustrated in Figure 4, the reactive distillation column 70 has two feeds 80, 82 and uses two catalyst zones, identified as an upper zone 72 containing the catalyst A 74 and a lower catalyst zone 76 containing the catalyst B 78. The top feed stream 80 is fed to the top of the column 70 (top feed stream). The upper feed stream 80 can comprise one or more alpha hydrogen alcohols. Bottom feed stream 82 is fed to the bottom of column 70 (bottom feed stream). Lower feed stream 82 may comprise hydrogen. The molar ratio of the one or more alpha hydrogen alcohols to hydrogen can be within any of the ranges described above with respect to Figure 3(a) (for example, from about 1:10 to about 1000:1 and all subs). -tracks). Alpha hydrogen alcohol can react in the upper catalyst (Catalyst A 74) to produce one or more higher alcohols and water. Examples of suitable higher catalysts are described in more detail herein with respect to higher alcohol conversion catalysts. As with the previous schematic designs shown, column 70 will usually include an upper stage or non-reactive rectifier section 71 and a lower stage or non-reactive withdrawal section 79.
[0073] Due to boiling point differences, water can move to the top of column 70 and higher alcohols can move to the bottom of column 70. By-products such as acetaldehyde, n-butyraldehyde and ethyl ether can be produced during the reaction and can move up to column 70. At least a portion of the by-products, if present, may be condensed in condenser 84 and recycled back to the reaction zone through reflux tank 86. The by-products produced in reaction may have boiling points close to the boiling point of one or more of the higher alcohols. The lower hydrogen feed stream 82 is useful in hydrogenating the by-products in the lower catalyst (Catalyst B) to produce components that can be easily separated from one or more of the higher alcohol products. Examples of hydrogenation catalysts (Catalyst B) are described in more detail in this. Product stream 81 comprising water from the reaction leaves the top of column 70. In one embodiment, product stream 81 may further comprise unreacted alpha hydrogen alcohol. Product stream 81 comprising alpha hydrogen alcohol and water can be fed to a dehydration unit to produce a stream of dehydrated alpha hydrogen alcohol, which can then be recycled back to column 70 as feed (eg as part of the stream power supply 80). A portion removed from the bottom is withdrawn as a product stream 92, while the remaining portion is passed through a reheater 90 to be recycled to a column 70. In one embodiment, the withdrawal from the bottom may be passed through a reheater (e.g., similar to reheater 90) and optionally passed to a separator where the portion of steam can pass to a column 70 while at least a portion of the remainder is withdrawn as the product streams of higher alcohols 92. The stream passes through a reheater 90 provides the evaporation and vapor flow effect for operating column 70. Product stream 92 can comprise the higher alcohols produced in the column along with unreacted alpha hydrogen alcohols and potentially any by-products produced by the reaction. Subsequent purification of the product stream 92 comprising higher alcohols may be necessary to remove hydrogenated by-products from the higher alcohols, for example using a separator such as that shown in Figure 2 as separator 32, which in one embodiment may comprise a distillation column.
[0074] In one embodiment, column 70 may operate under any of the conditions (e.g., operating pressure, operating temperature, etc.) discussed herein with respect to column 10 in Figure 1(b). Furthermore, column 70 may have any number of stages and in one embodiment column 70 may have any number of stages as described with respect to column 10 in Figure 1(b).
[0075] In the dual feed systems described above with respect to Figures 3(a) and 4, the hydrogen feed must be at a sufficiently low level that it does not significantly adversely affect the dehydration of the alpha hydrogen alcohols in the above zone while being effective to hydrogenate unwanted near-boiling by-products. Hydrogen feed rates can be adjusted empirically to optimize this balance. Generally, the ratio of alpha hydrogen:hydrogen alcohols can range from about 500:1 to 1:1 molar ratio, more generally about 500:1 to 10:1 or 500:1 to 100:1.
[0076] In one embodiment, the system of Figure 4 can also be used to co-produce one or more higher alcohols and ethyl acetate. In general, the process described above with regard to a production of one or more higher alcohols from a feed comprising one or more alpha hydrogen alcohols in Figure 4 will be the same or similar when co-production of higher alcohols and ethyl acetate is desired . As a result, similar elements will not be described with reference to Figure 4 in the interest of brevity. As schematically illustrated in Figure 4, the reactive distillation column 70 comprises two feeds 80, 82 and uses of two catalyst zones, identified as an upper zone 72 containing catalyst A 74 and a lower catalyst zone 76 containing catalyst B 78 The top feed stream 80 is fed to the top of the column 70 (top feed stream). Hydrogen feed stream 82 is fed to the bottom of column 70 (bottom feed stream). The alpha hydrogen alcohols present in the upper feed stream 80 can react in the upper catalyst (Catalyst A 74) to produce one or more higher alcohols, ethyl acetate, water and hydrogen. Examples of suitable superior catalysts are described in more detail herein with regard to conversion catalysts.
[0077] Due to boiling point differences, water and hydrogen can move towards the top of column 70 while the higher alcohols and ethyl acetate can move towards the bottom of column 70. By-products can moving in a column 70. A portion withdrawn from the bottom is withdrawn as a product stream from the higher alcohols and ethyl acetate 92, while the remaining portion is passed through a reheater 90 to be recycled to a column 70. In a In one embodiment, the bottom withdrawal can be passed through a reheater (e.g. similar to reheater 90) and optionally passed to a separator where the steam portion can pass to a column 70 while at least a portion of the remainder is withdrawn. as a product stream from the higher alcohols and ethyl acetate 92. The product stream from the higher alcohols and ethyl acetate 92 may comprise the higher alcohols and ethyl acetate produced in an alcohol. join together with unreacted alpha hydrogen alcohols and potentially any by-products produced by the reaction. Subsequent purification of the product stream 92 comprising the higher alcohols and ethyl acetate may be necessary to remove the hydrogenated by-products from the higher alcohols and ethyl acetate, for example using a separator such as that shown in Figure 2 as a separator 32, which in one embodiment may comprise a distillation column.
[0078] In one embodiment, one or more secondary reactors may be connected to a reactive distillation column to increase a catalyst impediment to improved reactant conversion. In the secondary reactor embodiment, the secondary reactor feed is withdrawn from the distillation column and the reactor effluent is returned to the same column again. An adequate amount of catalyst can be disposed in a reactor side system where traditional reactor types and catalyst structures can be used. Also, reaction conditions inside the secondary reactor such as temperature can be adjusted independently of those prevailing in the distillation column by the appropriate heat exchanger. In addition, the flow rates of the secondary reactors can be selectively controlled to provide a desired space velocity through the secondary reactor.
[0079] The schematics for a secondary reactor reactive distillation column with a single higher alcohols conversion catalyst are shown in figure 5. A simple secondary reactor is shown, however multiple secondary reactors along with the length of the reactive distillation column can be used. Figure 5(a) shows a configuration where the feed stream 93 to the secondary reactor 94 is turned over and phased to steam. In one embodiment, alpha hydrogen alcohols can react on the catalyst within secondary reactor 94 in the vapor phase. The output of secondary reactor 94 is stream 95 which is sent back to distillation column 40 at any location in column 40 above the location of feed stream 93. Figure 5(b) shows a configuration where feed stream 96 to the secondary reactor 97 is turned over and the liquid phase. In one embodiment, alpha hydrogen alcohols can react on the catalyst within secondary reactor 97 in the liquid phase. The output of secondary reactor 97 is stream 98 which is sent back to distillation column 40 at any location in column 40 below the location of feed stream 96. Secondary reactors 94 and 97 each contain one or more conversion catalysts of the higher alcohols to convert the alpha hydrogen alcohols to one or more higher alcohols. Examples of suitable higher alcohol conversion catalysts are described in more detail herein. In some embodiments, only one or more of the secondary reactors can comprise a catalyst and here they cannot be a catalyst located within reactive distillation column 40.
[0080] The use of a secondary reactor using a liquid feed can allow for the reaction to take place in the liquid phase. While not intended to be bound by theory, it is believed that dehydration of an alpha hydrogen alcohol (eg, ethanol) to produce a higher alcohol (eg, butanol) can occur in the higher alcohol conversion catalysts described herein in the liquid phase. The use of liquid phase reaction can allow for reactive distillation to be effectively used to convert alpha hydrogen alcohol to one or more higher alcohols and water.
[0081] While illustrated as an overturned vapor phase design and overturned liquid phase design in figures 5(a) and 5(b), the secondary reactors 94, 97 can also operate overturned using a liquid phase withdrawal from of column 40 and overturned using a vapor phase withdrawal from the column with appropriate equipment such as pumps, compressors, valves, piping, etc. In one embodiment, the secondary reactors 94, 97 can be implemented as a single reactor vessel, or as a plurality of reactor vessels arranged in series and/or parallel. In one embodiment, a plurality of secondary reactors can be implemented as shown in Figures 5(a) and 5(b) along with column length as required. In addition, when both column 40 and secondary reactor 94 comprise the catalysts, the higher alcohol conversion catalyst in both column 40 and secondary reactor 94 can convert the alpha hydrogen alcohols to one or more higher alcohols through the catalysts. specific higher alcohol conversion (e.g., catalyst compositions, catalyst forms, catalyst component loadings, or any combinations thereof) in each of column 40 and secondary reactor 94, 97 can be the same or different. Suitable higher alcohol conversion catalysts for converting alpha hydrogen alcohols to higher alcohols can be selected based on expected operating conditions, which may vary between column 40 and secondary reactor 94, 97. In some embodiments, Product selection can be adjusted through the use of catalyst selection in column 40 and secondary reactor 94, 97. For example, the higher alcohol conversion catalyst in column 40 can be configured to produce one or more butanol isomers and the higher alcohol conversion catalyst in the secondary reactor 94, 97 can be configured to produce an alcohol having a heavier molecular weight than butanol. To control the flow of fluids within the column, the product distribution can be adjusted to produce more or less butanol, or correspondingly more or less of the heavier molecular weight alcohols.
[0082] In one embodiment, each of the systems of Figures 5(a) and 5(b) can be used to co-produce a higher alcohol and/or ethyl acetate including the conversion catalysts described herein. In general, the processes described above with respect to producing one or more higher alcohols from a feed comprising one or more alpha hydrogen alcohols in Figure 5 will be the same or similar when co-production of higher alcohols and ethyl acetate is desired. As a result, similar elements will not be described with reference to Figure 5 in the interest of brevity. In general, the production system can be the same as the system for producing the higher alcohols from the alpha hydrogen alcohol feed, except that the catalyst can be used to co-produce one or more higher alcohols and ethyl acetate from the feed. of alpha hydrogen alcohol. In one embodiment, secondary reactors 94 and 97 can contain the conversion catalyst to convert the alpha hydrogen alcohol in the feed to one or more higher alcohols and/or ethyl acetate. Examples of suitable conversion catalysts are described in more detail herein. In some embodiments, secondary reactors 94, 97 can comprise a plurality of catalysts to produce one or more higher alcohols and ethyl acetate. For example, secondary reactors 94, 97 can comprise a higher alcohol conversion catalyst and an ethyl acetate conversion catalyst. In some embodiments, the catalyst in column 40 or secondary reactors 94, 97 can be the same or different. In some embodiments, only one or more of the secondary reactors can comprise a catalyst and here they cannot be a catalyst located within the reactive distillation column. Suitable conversion catalysts for converting ethanol to butanol and ethyl acetate can be selected based on expected operating conditions, which may vary between column 40 and secondary reactor 94, 97.
[0083] The schemes for a reactive distillation secondary reactor with two feeds and using the two catalyst zones are shown in Figure 6. In this embodiment, an upper feed 80 of the alpha hydrogen alcohols can be fed to the upper catalyst zone 82 of hydrogen can be fed to the lower zone. A single secondary reactor is shown for each catalyst zone in reactive distillation column 70, however multiple secondary reactors along with the length of reactive distillation column 70 can be used for each catalyst zone. Figure 6(a) shows a configuration where the feed stream from the upper zone 99 to the secondary reactor 100 is turned over and vapor phase. The feed stream from the lower zone 102 to another secondary reactor 103 is also turned over and vapor phase. The output of secondary reactor 100 is current 101 which is sent back to the distillation column at any location in the column above the location of feed stream 99. The output of secondary reactor 103 is current 104 which is sent back to the column of distillation at any location in the column above the location of the feed stream 102.
[0084] Figure 6(b) shows a configuration where the feed current from the upper zone 105 to the secondary reactor 106 is turned over and liquid phase. The feed stream from the lower zone 108 to another secondary reactor 109 is also turned over and liquid phase. The output of secondary reactor 106 is current 107 which is sent back to the distillation column at any location in the column below the location of feed stream 105. The output of secondary reactor 109 is current 110 which is sent back to the column of distillation at any location in the column below the feed stream location 108. Examples of catalysts suitable for secondary reactors 100 and 106 may include any of the higher alcohol conversion catalysts described in more detail herein. Examples of hydrogenation catalysts for secondary reactors 103 and 109 include any of the hydrogenation catalysts described in more detail herein. In some embodiments, only one or more of the secondary reactors can comprise a catalyst and here they cannot be a catalyst located within the reactive distillation column.
[0085] While illustrated as an overturned vapor phase design and an overturned liquid phase design in figures 6(a) and 6(b), the secondary reactors 100, 103, 106, 109 can also operate overturned using an overhead withdrawal. liquid phase from column 70 and turned over using a vapor phase withdrawal from column 70 with appropriate equipment such as pumps, compressors, valves, piping, etc. In one embodiment, the secondary reactors 100, 103, 106, 109 can be implemented as a single reactor vessel, or as a plurality of reactor vessel arranged in series and/or parallel. In one embodiment, a plurality of side reactors can be implemented as shown in Figures 6(a) and 6(b) along with the length of the column as required. In addition, the respective higher alcohol conversion catalysts in both column 70 and secondary reactors 100, 106 can convert a feed comprising the alpha hydrogen alcohol into one or more higher alcohols, through specific higher alcohol conversion catalysts (by example, catalyst compositions, catalyst forms, catalyst component loadings, or any combinations thereof) in each of column 40 and secondary reactors 100, 106 may be the same or different. Suitable higher alcohol conversion catalysts for converting alpha hydrogen alcohol to higher alcohols can be selected based on expected operating conditions, which may vary between column 40 and secondary reactors 100, 106. Similarly, the respective catalysts in both column 70 and secondary reactors 103, 109 may comprise hydrogenation catalysts, through specific catalysts (e.g. catalyst compositions, catalyst forms, catalyst component loadings, or any combinations thereof) in each of column 70 and secondary reactors 103 , 109 may be the same or different. The suitable hydrogenation catalyst can be selected based on expected operating conditions, which may vary between column 70 and secondary reactors 100, 106.
[0086] In one embodiment, each of the systems of Figures 6(a) and 6(b) can be used to co-produce one or more higher alcohols and/or ethyl acetate including the conversion catalysts described therein. The schemes for a reactive distillation of the secondary reactor with two feeds and the use of two distinct catalyst zones are shown in figure 6. In general, the process described above with respect to the production of one or more higher alcohols from the feed comprising a or more alpha hydrogen alcohols in figure 6 will be the same or similar when co-production of higher alcohols and ethyl acetate is desired. As a result, similar elements will not be described with reference to Figure 6 in the interest of brevity. In general, the system can be the same as the system for producing the higher alcohols from the alpha hydrogen alcohol feed, except that the catalyst can be used to produce one or more higher alcohols and/or ethyl acetate from the feed. of alpha hydrogen alcohol. Examples of suitable catalysts for secondary reactors 100 and 106 may include any of the conversion catalysts described in more detail herein. Examples of hydrogenation catalysts for secondary reactors 103 and 109 include any of the hydrogenation catalysts described in more detail herein. In some embodiments, only one or more of the secondary reactors can comprise a catalyst and here they cannot be a catalyst located within the reactive distillation column.
[0087] In the reactive distillation systems of Figures 5(a), 5(b), 6(a) and 6(b), the composition of the product stream 58, 92 can be adjusted by controlling the flow rate between the column of reactive distillation 40, 70 and the secondary reactors 94, 97, 100, 103, 106, 109. In one embodiment, a system for producing higher alcohols and/or ethyl acetate comprises a reactive distillation column 40, 70 loaded with one or more higher alcohol conversion catalysts and one or more secondary reactors 94, 97, 100, 106 loaded with one or more conversion catalysts. During continuous operation, flow rates 93/95, 96/98, 99/101, 105/107 between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 can be adjusted to achieve a composition desired product stream 58, 92. Flow rates 93/95, 96/98, 99/101, 105/107 between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 can be increased to decrease the production of one or more higher alcohols relative to ethyl acetate (for example, the ratio of higher alcohols to ethyl acetate), or decreased to increase the production of the higher alcohols relative to ethyl acetate. Alternatively, the flow between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 can be cut off to produce the product stream 58, 92 of pure or substantially pure higher alcohols. In one embodiment, flow rate adjustments 3/95, 96/98, 99/101, 105/107 are made by a control system.
[0088] In another embodiment, a system for the production of one or more higher alcohols (e.g., butanol) and/or ethyl acetate comprises a reactive distillation column 40, 70 loaded with one or more conversion catalysts and one or more secondary reactors 94, 97, 100, 106 are charged with one or more conversion catalysts. During continuous operation, the flow rates 3/95, 96/98, 99/101, 105/107 between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 can be adjusted to achieve a composition desired product stream 58, 92. Flow rates 3/95, 96/98, 99/101, 105/107 between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 can be increased to increase the production of a higher alcohol with respect to ethyl acetate or decreased to decrease the production of a higher alcohol with respect to ethyl acetate. When flow rates 3/95, 96/98, 99/101, 105/107 between column 40, 70 and one or more secondary reactors 94, 97, 100, 106 are cut off the production of ethyl acetate with respect to an output of one or more of the higher alcohols is maximized. In one embodiment, adjustments to flow rates 3/95, 96/98, 99/101, 105/107 can be made by a control system.
[0089] In one embodiment, a system for producing one or more higher alcohols may comprise a reactive distillation column 40, 70 loaded with a higher alcohol conversion catalyst suitable for use with an alpha hydrogen alcohol feed pure or substantially pure and one or more secondary reactors 94, 97, 100, 106 loaded with a higher alcohol conversion catalyst suitable for use with a feed of one or more alpha alcohol hydrogen and water. Alternatively, the reactive distillation column 40, 70 can be loaded with a superior alcohol conversion catalyst suitable for use with a feed of the alpha alcohols hydrogen and water and one or more secondary reactors 94, 97, 100, 106 can be loaded with a superior alcohol conversion catalyst suitable for use with pure or substantially pure alpha hydrogen alcohol. If the feed is pure or substantially pure alpha hydrogen alcohol, the flow rates 3/95, 96/98, 99/101, 105/107 between column 40, 70 and secondary reactors 94, 97, 100, 106 may be adjusted to maximize production of the higher alcohols by increasing flow through reactors having a catalyst suitable for use with pure or substantially pure alpha hydrogen alcohols, decreasing flow through the reactor having catalyst suitable for use with alpha hydrogen alcohols and water or a combination thereof. If the feed comprises alpha hydrogen and water alcohols, the flow rates 3/95, 96/98, 99/101, 105/107 between column 40, 70 and secondary reactors 94, 97, 100, 106 can be adjusted to maximize the production of the higher alcohols by increasing the flow through the column or reactors having the catalyst suitable for use with the alpha alcohols hydrogen and water, decreasing the flow through the column or reactors having the catalyst suitable for use with the alpha alcohols pure or substantially pure hydrogen or a combination thereof. In one embodiment, adjustments of flow rates 3/95, 96/98, 99/101, 105/107 can be made by a control system. In one embodiment, flow rates 102/104, 108/110 can be increased or decreased to reduce or eliminate one or more unwanted by-products from a product stream 58, 92. In one embodiment, adjustments of the 102/104, 108/110 flow rates are done by a control system.
[0090] As a general proposition, the number of side reactors and the type of catalyst with which the column and each secondary are individually loaded can be selected to accommodate a desired variety of feed stocks, a desired range of product compositions, or a combination of them during the operation of the reactive distillation column. During continuous operation, flow rates between the secondary reactors and the column can be adjusted (eg, selectively adjusted) to respond to changes in feed stock, to achieve a desired product composition, or a combination thereof. The ability to adjust flow rates between the secondary reactors and the column advantageously allows feed stocks to be shifted when market fluctuates in price and availability for the use of a feed stock having a different composition (eg quality smaller, higher water content, different mixture of alpha hydrogen alcohols, etc.). The ability to adjust flow rates between the secondary reactors and the column advantageously allows feed quality to be maintained despite fluctuations in feed stock composition during continuous operation. The ability to adjust and/or control flow rates between the secondary reactors and the column can also allow for the reduction or elimination of unwanted by-products to advantageously increase the purity of the desired products.
[0091] As schematically illustrated in Figure 7(a), the process for producing the higher alcohols may comprise a product separation section 212 for use in separating a product stream allowing at least a portion of any unreacted ethanol to be recycled at the input of the process. The product separation section can be configured to provide at least one product stream comprising a simple reaction product such as a higher alcohol (eg, propanol, butanol, hexanol, etc.), ethyl acetate, butyl acetate , or another reaction product having a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99% or more than about 99.5% by weight. In one embodiment, a separation train can be used to produce a plurality of streams that each predominantly comprise a single reaction product such as a higher alcohol (e.g., propanol, butanol, hexanol, etc.), acetate and ethyl, butyl acetate, or other reaction product having a purity of more than about 90%, more than about 95%, more than about 96%, more than about 97%, more than about 98%, more than about 99%, or more than about 99.5% by weight. At least one additional stream can be produced comprising the remaining components of the product stream from the reactive distillation column. In one embodiment, the plurality of streams are produced in the separation section which comprises a stream predominantly comprising butanol, a stream predominantly comprising propanol, a stream predominantly comprising hexanol, a stream predominantly comprising ethyl acetate, a stream which comprises water, a stream which comprises ethanol, a heavier stream which comprises one or more products of reaction with boiling points above the boiling point of hexanol, or any combinations thereof. In one embodiment, a stream comprising ethanol, if present, can be recycled to the reactive distillation column. In one embodiment, at least a portion of the stream comprising water can be recycled into the reactive distillation column to provide at least a portion of feed water.
[0092] As schematically illustrated in Figure 7(a), a system 200 for producing one or more higher alcohols may comprise a feed stream 202 comprising an alpha hydrogen alcohol which may optionally be combined with a recycle stream 220 comprising a alpha hydrogen alcohol to form an inlet stream 204 to reactive distillation system 206. System 200 may be useful for embodiments where there is incomplete conversion of an alpha hydrogen alcohol in reactive distillation system 206. While illustrated as being combined prior to introduction to the reactive distillation system 206, a feed stream 202 and a recycle stream 220 can be fed individually to the reactive distillation system 206. In one embodiment, the reactive distillation system 206 can comprise any one of reactive distillation systems described with respect to Figures 1-6 herein. The reactive distillation system 206 can produce an upper product stream 208 and a lower product stream 210. The upper product stream 208 may comprise water, hydrogen, unreacted alpha hydrogen alcohols or a combination thereof and may generally correspond to any one of streams 11, 47 and/or 81 as illustrated in Figures 1-6. Similarly, a lower product stream 210 may comprise higher alcohols (e.g., butanol, 1-hexanol, 1-octanol, 2-ethyl-1-butanol, 2-ethyl-1-hexanol, butanediol, etc.), acetate ethyl, butyl acetate, ethyl butyrate, 2-pentanone, propanol, additional reaction products, possibly water and/or any combination thereof. In one embodiment, a lower product stream 210 may correspond to any of the streams 22 , 36, 58 and/or 92 as illustrated in Figures 1-6.
[0093] An optional upper separation section 250 may receive upper product stream 208 from reactive distillation system 206. Upper separation section 250 may be configured to separate water from any of the alpha hydrogen alcohols ( eg ethanol) in the upper product stream 208, which may be present in a water-alcohol azeotrope such as a water-ethanol azeotrope, allowing the alpha hydrogen alcohol feed to be recycled to the system while removing water to conduct the reaction within the reactive distillation system 206. The upper separation section 250 may comprise any number or type of separation units, which may utilize temperature and/or pressure swing distillation, temperature and/or pressure swing adsorption , membrane-based separation, molecular sieve separation, any other suitable separation technology, or any combination thereof, all of which can be used. to remove a desired amount of water from the upper product stream 208. The upper separation section 250 can produce the recycle stream 254 which comprises one or more alpha hydrogen alcohols and an output stream 252 which comprises water. Recycle stream 254 may comprise the alpha hydrogen alcohols for use as a feed to reactive distillation system 206. In some embodiments, alpha hydrogen alcohol stream 254 cannot be recycled to the reactive distillation system, but rather, it may exit system 200 as a separate product stream. While illustrated as being combined prior to introduction to reactive distillation system 206, a feed stream 202 and a recycle stream 254 (as well as recycle stream 220) can be fed individually to the reactive distillation system 206.
[0094] A product separation section 212 may receive the lower product stream 210 from the reactive distillation system 206 and, in some embodiments, the upper product stream 208. The product separation section 212 may comprise any number or type of separation units, which may use temperature and/or pressure swing distillation, temperature and/or pressure swing adsorption, membrane-based separation, cryogenic distillation, any other suitable separation technology, or any combination of these, all of which can be used to generate a distribution of the desired product. The product separating section 212 may generally produce one or more product streams such as product stream 216. The higher alcohol product stream 216 may comprise a higher alcohol having a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% by weight. In addition to a higher alcohol product stream 216, one or more additional streams may be produced by the product separation section 212. In one embodiment, light product streams 214 may be produced. Light product streams 214 can comprise water, any alpha hydrogen alcohol from feed, ethyl acetate, other light components, or any combination thereof. In one embodiment, heavier product streams 218 can comprise one or more reaction products (e.g., one or more aldehydes, ketones, heavy alcohols, any combination thereof, etc.). In one embodiment, a recycle stream 220 can be produced. The recycle stream can comprise one or more alpha hydrogen alcohols for use as a feed to the reactive distillation system 206. In some embodiments, the alpha hydrogen alcohols stream cannot be recycled to the reactive distillation system, but before it can exit system 200 as a separate product stream. Each of the potential product streams 214, 216, 218 and/or 220 may exit the system as a separate product stream and/or exit the system 200 for use as a fuel and/or as a feed to additional downstream products. While illustrated as separate streams 214, 216, 218 and/or 220, one or more of these streams may exit system 200 as a combined product stream.
[0095] As schematically illustrated in Figure 7(b), a process for producing the higher alcohols and ethyl acetate may comprise a product separation section for use in separating the product stream and allowing for at least a portion of either alcohol of unreacted alpha hydrogen in the feed to be recycled into the process input. The product separation section may be configured to provide at least one product stream comprising a higher alcohol and at least one product stream comprising ethyl acetate. The product stream comprising the higher alcohol may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% by weight. The product stream comprising ethyl acetate may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% ethyl acetate by weight. At least one additional stream can be produced which comprises the remaining components of the product stream from the reactive distillation column. In one embodiment, a plurality of streams are produced in the separation section comprising one or more streams predominantly comprising individual higher alcohols, a stream predominantly comprising ethyl acetate, a stream comprising water, a stream comprising hydrogen, a stream comprising one or more alpha hydrogen alcohols, a heavier stream comprising one or more reaction products with boiling points above the boiling points of the separate higher alcohols and/or ethyl acetate, or any combination thereof. In one embodiment, the stream comprising the alpha hydrogen alcohols can be recycled to the reactive distillation column. In one embodiment, at least a portion of the stream comprising water can be recycled into the reactive distillation column to provide at least a portion of a water feed. In one embodiment, at least a portion of the hydrogen-comprising stream may be recycled to the reactive distillation column to provide at least a portion of the hydrogen feed.
[0096] As schematically illustrated in Figure 7(b), a system 201 for producing higher alcohols and ethyl acetate can comprise a feed stream 202 comprising one or more alpha hydrogen alcohols that can be combined with a recycle stream 220 comprising at least one alpha hydrogen alcohol to form an inlet stream 204 to the reactive distillation system 206. The system 201 may be useful for embodiments where there is incomplete conversion of the alpha hydrogen alcohols in the reactive distillation system 206 While illustrated as being combined prior to introduction to reactive distillation system 206, a feed stream 202 and a recycle stream 220 may be fed individually to reactive distillation system 206. In one embodiment, reactive distillation system 206 can comprise any of the reactive distillation systems described with respect to Figures 1-6 herein. The reactive distillation system can produce upper product streams 208 and 209 and a lower product stream 210. Upper product stream 208 may comprise water, hydrogen and at least a portion of any unreacted alpha hydrogen alcohols, and may generally correspond to any one of streams 11, 47 and/or 81 as illustrated in Figures 1-6. Upper product stream 209 may comprise hydrogen and may generally correspond to any one of streams 19, 59 and/or 88 as illustrated in Figures 1-6. Lower product stream 210 may comprise the higher alcohols, ethyl acetate, additional reaction products, or any combination thereof, and lower product stream 210 may generally correspond to any of streams 22, 36, 58 and/or 92 as illustrated in Figures 1-6.
[0097] An optional upper separation section 250 can receive the upper product stream 208 from the reactive distillation system 206. The upper separation section 250 can be configured to separate water from any alpha hydrogen alcohols in the water stream. upper product 208, which may be present in a water-alcohol azeotrope, to allow any alpha hydrogen alcohols to be recycled to the system while removing water to drive the reaction within the reactive distillation system 206. The upper separation section 250 may comprise any number or type of separation units, which may use temperature and/or pressure swing distillation, temperature and/or pressure swing adsorption, membrane-based separation, molecular sieve separation, any other separation technology water, or any combination thereof, all of which can be used to remove a desired amount of water from the current. and upper product 208. Upper separation section 250 can produce recycle stream 254 which comprises any alpha hydrogen alcohols and an output stream 252 which comprises water. Recycle stream 254 may comprise an alpha hydrogen alcohol for use as a feed to reactive distillation system 206. In some embodiments, alpha hydrogen alcohol stream 254 cannot be recycled to the reactive distillation system, but rather can exit system 200 as a separate product stream. While illustrated as being combined prior to introduction to reactive distillation system 206, a feed stream 202 and a recycle stream 254 (as well as recycle stream 220) can be fed individually to the reactive distillation system 206.
[0098] Product separation section 212 may receive lower product stream 210 from reactive distillation system 206 and, in some embodiments, upper product stream 208. Product separation section 212 may comprise any number or type of separation units, which may use temperature and/or pressure swing distillation, temperature and/or pressure swing adsorption, membrane-based separation, cryogenic distillation, any other suitable separation technology, or any combination of these, all of which can be used to generate a distribution of the desired product. The product separation section 212 can generally produce one or more higher alcohol product streams 216, an ethyl acetate product stream 217, or a combination thereof. The one or more current product higher alcohols 216 may each comprise an individual higher alcohol having a purity of greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% by weight. The current product 216 ethyl acetate can comprise ethyl acetate having a purity of greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than than about 98%, greater than about 99%, or greater than about 99.5% ethyl acetate by weight. In addition to the one or more higher alcohol product streams 216 and the ethyl acetate product stream 217, one or more additional streams may be produced by the product separation section 212. In one embodiment, the light product streams 214 can be produced. Light product streams 214 can comprise water, hydrogen, an alcohol alpha hydrogen, other light components, or any combination thereof. In one embodiment, heavier product streams 218 can comprise one or more reaction products (e.g., one or more aldehydes, ketones, other alcohols, any combination thereof, etc.). In one embodiment, a recycle stream 220 can be produced. The recycle stream may comprise an alpha hydrogen alcohol for use as a feed to the reactive distillation system 206. In some embodiments, the alpha hydrogen alcohol stream cannot be recycled to the reactive distillation system, but rather can exit the system 200 as a separate product stream. Each of the potential product streams 214, 216, 217, 218 and/or 220 may exit the system as a separate product stream and/or exit the system 200 for use as a fuel and/or as a feed to additional downstream products. While separate streams 214, 216, 217, 218 and/or 220 are illustrated, one or more of these streams may exit system 220 as a combined product stream.
[0099] The production process of higher alcohols, with or without the production of ethyl acetate, can produce a variety of products. For example, the process can produce one or more higher alcohols such as butanol, propanol, 1-hexanol, 1-octanol, 2-ethyl-1-butanol, 2-ethyl-1-hexanol, butanediol and heavier alcohols. The process can also produce various additional products such as ethyl acetate, butyl acetate, ethyl butyrate, 2-pentanone, propanol and/or water. Various by-products can also be produced that can result in a complex mixture of components that can be difficult to separate. This complex mixture may exhibit a number of binary azeotropes, ternary azeotropes and possibly azeotropes containing four or more components. Some of the azeotropes may be homogeneous, while others may be heterogeneous. These azeotropes can give rise to distillation limits in the composition space which, together with azeotropes, act as barriers to distillation and limit the ability to achieve high recovery and/or purity of the desired products using distillation alone. So water is present in a sufficient amount, the system may also comprise a multiple liquid phase region, with internal lines of vapor-liquid-liquid and/or liquid-liquid equilibrium that cross some of these boundaries. In some embodiments, a product separation system can exploit its system characteristic and comprises a separation sequence comprising distillation columns and decanters. This system may be capable of producing one or more high purity product streams such as one or more high purity higher alcohol streams, an ethyl acetate stream and potentially one or more other valuable by-product streams.
[00100] In one embodiment, a separation process may be indicated to separate ethyl butyrate, a valuable reaction by-product, from the mixture of a higher alcohol such as butanol and water. The residue curve map for the mixture is illustrated in Figure 8 and shows that just as one system exhibits three low-boiling binary azeotropes, of which two (water - butanol and water - ethyl butyrate) are heterogeneous, while the third azeotrope binary (butanol - ethyl butyrate) is homogeneous. The system also exhibits a heterogeneous ternary low boiling azeotrope. These azeotropes are elevation to the three limits of distillation, which divides the composition space into three distinct regions. The system also exhibits a heterogeneous region and some of the liquid-liquid internal equilibrium lines crossing one or more of the distillation limits. In this embodiment, the feed to the separation system can predominantly comprise butanol and the feed therefore is in the upper distillation region as shown in Figure 8. While the distillation must be used to recover the high purity butanol from this mixture , the presence of distillation limits restrict on total butanol recovery, as well as ability to recover high purity ethyl butyrate.
[00101] Various separation schemes can then be used to separate a complex mixture such as the product stream from the reactive distillation process described herein. One embodiment of the separation sequence for recovering high purity butanol, high purity ethyl butyrate, and water containing only minor amounts of the organic components is schematically illustrated in Figure 9. A 301 input stream comprising butanol, butyrate of ethyl, and water can be combined with a recycle stream 303 to form the combined stream 302. In this embodiment, ethyl butyrate is included representative species of other esters (e.g., ethyl esters, butyl esters, etc.) in terms of vapor-liquid behavior and additional esters (eg butyl acetate, ethyl acetate, etc.) may also be present in the system and can be expected to behave similarly. The presence of water in the inlet stream 301 can aid in the separation of butanol from ethyl butyrate, and water can be added to the inlet if a sufficient amount of water is not present. Combined inlet stream 302 can be fed to a first distillation column 304. Distillation column 304 can comprise any of the types of distillation columns described herein. Distillation column 304 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. Distillation column 304 can produce an upstream 308 and a downstream 306. Downstream 306 can comprise high purity butanol. For example, butanol recovered in the downstream may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% butanol by weight. While described as butanol, other higher alcohols, if present, can also be recovered in the 306 lower stream.
[00102] Upper stream 308 from first distillation column 304 may pass through heat exchanger 310 to at least partially condense an upper stream 308 and pass condensed stream 312 to a decanter 314. Heat exchanger 310 may understand any of the heat exchanger types described herein. Decanter 314 generally comprises any device capable of providing a liquid-liquid separation. Decanters can use devices such as dikes, downspouts, sedimentation chambers, internal heat exchangers and others to effect liquid-liquid separation. In some embodiments, a decanter may also provide an outgoing stream of steam or the steam, if present, may be exhausted with one of the liquid streams. In this embodiment, decanter 314 can provide a separation of a liquid phase predominantly comprising water from the organic phase comprising ethyl butyrate. A fraction of the organic phase and possibly a fraction of the aqueous phase may be refluxed in the decanter column 314 as reflux stream 311. The remainder of the aqueous phase, which may comprise water and a relatively minor amount of dissolved organics, may be recovered and discharged from the system as a stream of water 316. The portion of the organic phase not refluxed to distillation column 304 may be passed to a second distillation column 320. Second distillation column 320 may comprise any of the types of distillation columns described herein and the second distillation column 320 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. Second distillation column 320 may produce an upper stream 322 and a lower stream 324. A portion of the lower stream 324 may be passed through an exchanger to provide a steam feed to the column and the remaining portion may comprise high purity ethyl butyrate . For example, the ethyl butyrate recovered in lower stream 324 may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than than about 98%, greater than about 99%, or greater than about 99.5% ethyl butyrate by weight. Upper stream 322 may comprise water and butanol. A portion of the upper stream 322 can be condensed and refluxed to a second distillation column 320 and the remaining portion can be recycled as recycle stream 303 to an inlet stream 301 and/or pass to the first distillation column 304. balance lines of the resulting material for this separation sequence are shown in Fig. 8.
[00103] Another embodiment of a separation scheme 350 for separating the components of a complex mixture is illustrated in Figure 10. In this embodiment, the separation sequence can be used to recover one or more streams of higher alcohol from high purity, an ethyl acetate stream and optionally one or more other valuable by-product streams. In this embodiment, an input stream 352 may first be passed to a settler 354. In one embodiment, an input stream 352 may be the product stream from any of the reactive distillation processes described herein. Input stream 352 may comprise a number of components including any of the products produced in the reactive distillation process described herein. In one embodiment, an input stream 352 to separation sequence 350 comprises one or more higher alcohols (e.g., propanol, butanol, 1-hexanol, 1-octanol, 2-ethyl-1-butanol, 2-ethyl- 1-hexanol, butanediol, octanol, decanol, dodecanol and heavier alcohols, etc.), ethyl acetate, butyl acetate, ethyl butyrate, 2-pentanone and possibly water. Inlet stream 352 may be passed through an optional inlet decanter 354 to remove any excess water that forms a separate liquid phase. The resulting water stream 356 comprising water and relatively minor amount of dissolved organics can be passed from decanter 354 and discharged from the process. When decanter 354 is used, decanter 354 can be operated near the bubble point of the mixing inlet stream 352 in order to minimize the amount of dissolved organics such as propanol and/or butanol in the aqueous phase.
The organic phase can exit the decanter 354 as liquid stream 358. The liquid stream 358 can be combined with a recycle stream 360 and the combined stream can be fed to a first distillation column 362. The first distillation column 362 can comprise any of the types of distillation columns described herein and the first distillation column 362 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. The first distillation column 362 may produce an upper stream 364 and a lower stream 366. A portion of the lower stream 366 may be passed through an exchanger to supply the steam feed to column 362 and the remaining portion may comprise one or more higher alcohols such as such as butanol, 1-hexanol and/or the other higher alcohols.
[00105] The bottom stream 366 from the first distillation column 362 may further be separated using one or more distillation columns to recover one or more high purity product streams. In one embodiment, the product streams can include product streams that predominantly comprise a simple higher alcohol. For example, further separation can produce product streams predominantly comprising butanol and/or possibly 1-hexanol and the remaining heavy alcohols can be produced individually or as a combined stream. In the embodiment shown in Figure 10, a lower stream 366 can be passed to a second distillation column 370. The second distillation column 370 can comprise any of the types of the distillation columns described herein and the second distillation column 370 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. Second distillation column 370 can produce a plurality of product streams. In one embodiment, second distillation column 370 can produce a butanol product stream 372 as the upper product, an intermediate side stream 376 predominantly comprising hexanol, and a lower stream comprising one or more higher alcohols having a point boiling point greater than that of hexanol (eg 1-hexanol). In one embodiment, the butanol recovered in the 372 butanol product stream may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97 %, greater than about 98%, greater than about 99%, or greater than about 99.5% butanol by weight. In some embodiments, one or more of the additional distillation columns can be combined with a first distillation column 362 and/or used further to purify the product streams from the second distillation column 370. For example, a further distillation column it should further be used to separate the individual components of the bottom product stream 374 from the second distillation column 370. In either dose column, the desired products can be recovered as one or more side streams. In some embodiments, side rectifier columns or side separator columns can also be used with the first distillation column 362 and/or the second distillation column 370 to improve the purity of the off-stream products.
[00106] Upper stream 364 from first distillation column 362 may pass through heat exchanger 366 to at least partially condense an upper stream 364. Heat exchanger 368 may comprise any of the described types of heat exchanger in this. The at least partially condensed stream 367 may be passed to a settler 368. In some embodiments, the settler 368 may comprise a series of settlers operating at the same or different temperatures. Decanters 368 can generate an aqueous stream and an organic stream. A fraction of the organic stream, and possibly a fraction of the aqueous stream, may be refluxed in a first distillation column 362. For example, stream 369 may comprise a portion of the organic stream and optionally, a portion of the aqueous stream. The remainder of the aqueous stream 369, which may comprise water with a relatively minor amount of dissolved organics, can be recovered and discharged from the system. As noted above, the presence of water can be important in facilitating the separation of two or more of the organic components in inlet stream 352. Consequently, a fraction of the aqueous stream 369 can also be recycled to first distillation column 362 and/or to a separation system 350 inlet stream 352 and/or combined stream 358. Additional water may be added to a first distillation column 362 and/or inlet stream 352 or combined stream 358 to facilitate a separation. Organic product stream 378 from decanter 368 can comprise one or more higher alcohols and additional by-products. In one embodiment, organic product stream 378 may comprise one or more higher alcohols such as propanol and/or butanol as well as one or more additional organic components such as ethyl acetate, butyl acetate, ethyl butyrate and/or 2-pentanone. Organic product stream 378 can also comprise water.
[00107] A number of alternative separation sequences can be used to recover any ethyl acetate, any remaining butanol and potentially some of the valuable by-products such as butyl acetate in organic product stream 378. In the embodiment illustrated in Fig 10, the organic product stream 378 can be sent to a distillation sequence which comprises a decanter. Organic product stream 378 may first pass to a third distillation column 380. Third distillation column 380 may comprise any of the types of distillation columns described herein and third distillation column 380 may operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. The third distillation column 380 can produce an upper stream 382 and a lower stream 384.
[00108] Upper stream 382 from third distillation column 380 may be condensed in a heat exchanger 386 to at least partially condense an upper stream 382. Heat exchanger 386 may comprise any of the described types of heat exchanger in this. The at least partially condensed stream may pass to a settler 388, or possibly a series of settlers operating at the same or different temperatures. Decanter 388 can produce at least one organic phase stream and one phase comprising the stream. At least a portion of the organic phase stream, and possibly also a fraction of the aqueous phase, may be refluxed to a third distillation column 380. The remainder of the aqueous phase stream 390, which may comprise relatively lesser amount of water. dissolved organics can be recovered and discharged from the system. The remainder of the 392 organic phase stream, which may comprise organics including, but not limited to, ethyl acetate in addition to a minor amount of water, may still be separated to recover high purity ethyl acetate. In some embodiments, an organic phase stream 392 can be recycled to one or more reactors as a reactant.
[00109] Separation of the organic phase stream 392 can be achieved using a simple distillation column (eg the fourth distillation column 4) as shown in Fig 10. The fourth distillation column 394 can comprise any of the types of distillation columns described herein and the fourth distillation column 394 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. The fourth distillation column 394 can produce an upper stream 398 and a lower stream 396. The lower stream 396 may comprise high purity ethyl acetate. In one embodiment, the ethyl acetate recovered in the lower stream may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% ethyl acetate by weight. Upper stream 398 may be passed to heat exchanger 386, where at least a portion of upper stream 398 may be condensed and passed to at least one of decanter 388 and/or third distillation column 380.
[00110] The bottom stream 384 from the third distillation column 380 can be passed to a fifth distillation column 400. The bottom stream 384 can generally comprise a mixture of the organics, which may include, but is not limited to, acetate. butyl, ethyl butyrate, propanol, 2-pentanone, butanol, butyl acetate and/or ethyl butyrate. Fifth distillation column 400 can comprise any of the types of distillation columns described herein and fifth distillation column 400 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0. 5 atm to about 40 atm. The fifth distillation column 400 can produce a plurality of streams comprising an upper stream 404, a lower stream 406 and/or one or more side streams of product 402. The lower stream 406 may comprise butyl acetate and/or ethyl butyrate . The upper stream may comprise propanol and/or 2-pentanone. The product side stream 402 may primarily comprise butanol, butyl acetate and/or ethyl butyrate. The by-product stream 402 can be recycled to a first distillation column 362, the feed 352, the combined stream 358 and/or decanter 368. In some embodiments, the fourth distillation column 394 and the fifth distillation column 400 can be combined in a single column operating at a pressure greater than about 3 atm and the butanol can be recovered as a by-product with an optional by-product rectifier used to improve the purity of the butanol product.
[00111] Another embodiment of the separation process 500 is illustrated in Figure 11. The separation process 500 is similar to the separation process 350 illustrated in Figure 10 with the exception that the lower product stream 384 from the third column of 380 distillation can pass to a different series of separation units. The remaining components of separation process 500 may be the same or similar to those described with respect to Figure 10 and similar components will not be described with respect to Figure 11 in the interest of brevity. In this embodiment, a lower stream 384 can pass to a fifth distillation column 500. The fifth distillation column 500 can comprise any of the types of the distillation columns described herein and the fifth distillation column 500 can operate at a pressure that ranges from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. The fifth distillation column 500 can produce an upper stream 502 and a lower stream 504. The upper stream 502 may comprise propanol and/or 2-pentanone.
[00112] The lower stream 504 from the fifth distillation column 500 may comprise butanol, ethyl butyrate and/or butyl acetate, and a lower stream 504 may pass to a sixth distillation column 506, which can operate at a pressure greater than about 3 atm. Sixth distillation column 506 can comprise any of the types of distillation columns described herein and sixth distillation column 506 can operate at a pressure ranging from about 3 atm to about 80 atm. In general, a butanol-butyl acetate azeotrope can limit the purity of any butanol recovered using distillation into a mixture of butanol and butyl acetate. However, the azeotrope is pressure sensitive and is not present at a pressure greater than about 3 atm. Operating the sixth distillation column at a pressure greater than about 3 atm can leave a higher current to comprise high purity butanol. In one embodiment, the butanol recovered in upper stream 508 may have a purity greater than about 90%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, or greater than about 99.5% butanol by weight. Bottom stream 510 may comprise butyl acetate and/or ethyl butyrate. In some embodiments, fourth distillation column 394 and fifth distillation column 500 can be combined into a single column operating at a pressure greater than about 3 atm and butanol can be recovered as a by-product with a rectifier optional secondary used to improve the purity of the butanol product.
[00113] Another embodiment of a 600 separation process is illustrated in Figure 12 for recovering a higher alcohol such as butanol from an organic phase stream from decanter 368. The 600 separation process is similar to the 350 separation process illustrated in Figure 10 with the exception that the organic phase stream from decanter 388 is recycled to a third distillation column 380 and a lower stream 600 from the third distillation column 380 may be passed to a different series of separation units. The remaining components of separation process 600 may be the same or similar to those described with respect to Figure 10 and similar components will not be described with respect to Figure 12 in the interest of brevity.
[00114] In this embodiment, an overhead stream from the third distillation column 380 may be at least partially condensed in heat exchanger 386 and passed to a decanter 388. The organic phase, and optionally a fraction of the aqueous phase, may be refluxed to a third distillation column 380. The remainder of the aqueous phase may pass out of decanter 388 and be discharged from the process as an aqueous phase stream 390. The aqueous phase stream 390 may predominantly comprise water as an amount smallest of dissolved organics.
[00115] In this embodiment, a lower stream 600 from the third distillation column 380 may pass to a fourth distillation column 602, where the lower stream 600 comprises organics that are substantially free of water. Fourth distillation column 602 can comprise any of the types of distillation columns described herein and fourth distillation column 602 can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0. 5 atm to about 40 atm. The fourth distillation column 602 can produce an upper stream 604 and a lower stream 606. The lower stream 606 may comprise butanol, butyl acetate and/or ethyl butyrate, as the remainder of the feed, which can potentially be added to a tank of gasoline, can be recovered as an upper stream 604. In one embodiment, an upper stream 604 may comprise ethyl acetate, propanol and/or 2-pentanone.
[00116] The bottom stream 606 from the fourth distillation column 602 can further be separated into a fifth distillation column 608. The fifth distillation column 608 can comprise any of the types of the distillation columns described herein and the fifth distillation column of 608 distillation can operate at a pressure ranging from about 0.1 atm to about 80 atm, or about 0.5 atm to about 40 atm. Fifth distillation column 608 can produce an upper stream 610 and a lower stream 612. Lower stream 612 may comprise butyl acetate and/or ethyl butyrate as the lower product. The upper stream 610, depending on the pressure at which the fifth distillation column 608 is operated, may comprise high purity butanol (e.g. when the pressure is greater than about 3 atm) or a mixture comprising predominantly of butanol, acetate of butyl and/or ethyl butyrate (eg when the pressure is below about 3 atm). Upper stream 610 can be recycled to a first distillation column 362, or inlet stream 352. In some embodiments, two or more of the columns (e.g., third distillation column 380, fourth distillation column 602 and /or the fifth distillation column 608) can be combined in the single column, with the desired streams recovered as side streams. In addition, secondary rectifiers/removals can be used to enhance the purity of secondary stream products.
[00117] Selection of the appropriate separation scheme can be based on the composition of the 352 input mixture, the composition of the desired products (for example, one or more high purity streams and/or one or more mixed streams) and/or the total process savings. Also, various modifications and alterations are considered when the relative proportion and compositions of the higher alcohols change. For example, the heavier alcohol stream 374 can still be separated in one or more separation steps when individual higher product alcohol streams are desired.
[00118] Suitable higher alcohol conversion catalysts and combinations thereof are capable of converting at least a portion of the one or more alpha hydrogen alcohols (for example, primary or secondary alcohols such as ethanol) in a feed stream to a product of higher value such as one or more higher alcohols. As noted above, higher alcohols refer to alcohols that have a higher molecular weight than the alcohol forming the reactant in the formation process (eg, C6-C13 alcohols, or higher alcohols). Higher alcohols can include n-butanol and other butanol isomers as well as significant amounts of 1-hexanol, 2-ethylbutanol, 1-octanol, 2-ethylhexanol and other higher alcohol isomers (eg, isomers of hexanol, octanol, decanol , dodecanol, etc.).
[00119] Suitable higher alcohol conversion catalysts can comprise any catalyst capable of performing a dehydration, dehydrogenation and dimerization aldol condensation reaction and can be used alone or in combination with additional catalytic materials in the reactors. In one embodiment, suitable higher alcohol conversion catalysts can generally comprise metals, oxides or salts, or any combination thereof, of copper, barium, rethenium, rhodium, platinum, palladium, rhenium, silver, cadmium, zinc, zirconium, other, thallium, magnesium, manganese, aluminum, chromium, nickel, iron, molybdenum, sodium, strontium, tin and mixtures thereof. In many cases, the butanol conversion catalyst material will be provided on a support material. The higher alcohol conversion catalyst can be treated with a carbonate (eg, sodium carbonate), reduced with hydrogen, and/or other suitable treatments before use.
[00120] In general, catalysts for the production of one or more higher alcohols can produce only the higher alcohols or both higher alcohols such as ethyl acetate. Catalysts suitable for producing higher alcohols with only trace amounts of by-products include Guerbet reaction catalysts, including but not limited to hydroxyapatite and Guerbet solid base reaction catalysts, solid base multi-component oxide catalysts, zeolites with alkaline counterions, magnesium oxide, or any combination thereof.
[00121] The higher alcohols conversion catalyst may comprise nickel or nickel oxide supported on alumina and the butanol conversion catalyst may have a nickel weight loading between about 2% and about 20%. The higher alcohols conversion catalyst may comprise coprecipitated catalysts represented by the formula: M/MgO/Al2O3, wherein M represents palladium, rhodium, nickel, or copper or oxides thereof
[00122] The higher alcohols conversion catalyst may comprise copper oxide powders, lead, zinc, chromium, molybdenum, tungsten, manganese, lead, salts thereof and any combination thereof. In one embodiment, the copper oxide conversion catalyst higher alcohols may comprise a zeolite with an alkali metal.
[00123] The catalyst for converting higher alcohols can comprise solid base catalysts and bifunctional solid base/acid catalysts. The higher alcohols conversion catalyst may comprise a hydroxyapatite represented by the formula Ca10(PO4)6(OH)2 wherein the ratio of calcium to phosphorus (Ca:P) is between about 1.5 and about 1.8 to non-stoichiometric hydroxyapatites. The higher alcohols conversion catalyst may comprise an apatite structure that satisfies the formula: Ma(M'Ob)cX2, where M represents calcium, strontium, magnesium, barium, lead, cadmium, iron, cobalt, nickel, or zinc , M' represents phosphorus, vanadium, arsenic, carbon or sulfur and X represents a fluorine, chlorine, bromine or a hydroxide. In one embodiment, a, b and c are the total numbers that balance the valence requirements of M, M', and X. In another embodiment, a is 10, b is 3, and c is 6. In another embodiment, Ma(M'Ob)cX2 is a non-stoichiometric apatite and a is about 10, b is about 3, c is about 6, and the ratio of a to c (a:c) is between about 1.5 and about 1.8. The higher alcohol conversion catalyst may comprise a basic calcium and/or magnesium phosphate compound including calcium and/or magnesium phosphates, phosphate carbonates, pyrophosphates or others. In one embodiment, the higher alcohols conversion catalyst may also comprise magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate (Mg3(PO4)2.8H2O), calcium oxide, calcium hydroxide, calcium fluoride, silicate of calcium (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite (Ca10(PO4)6F2), tetracalcium phosphate (eg Ca4(PO4)2O), hydrotalcite , talc, kaolin, sepiolite, or any combination thereof.
[00124] In certain embodiments, the higher alcohols conversion catalyst may include a catalyst support. The catalyst support stabilizes and supports the catalyst. The type of catalyst support used depends on the chosen catalyst and the reaction conditions. Suitable supports may include, but are not limited to, carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, zeolites, carbon nanotubes, carbon fullerene and any combination thereof.
[00125] The higher alcohol conversion catalyst can be used in any of the conventional types or structures known in the art. It can be used in the form of extrudates, globules, granules, broken fragments, or various special shapes. In one embodiment, consideration of the use of the higher alcohols conversion catalyst in the reactive distillation system and/or as a mass transfer surface within the distillation column can be taken into account when determining a suitable shape. For example, the higher alcohol conversion catalyst may be shaped similar to structured packaging material or suitable for insertion into structured packaging. When the higher alcohols conversion catalyst is used with one or more secondary reactors, the catalyst may be disposed within a reaction zone and the feed may be passed through the mixed phase, liquid or steam and flow in upward flow or descendant or internal or external.
[00126] In one embodiment, the higher alcohols conversion catalyst described herein may be able to achieve a relatively high conversion and/or selectivity of an alpha hydrogen alcohol to one or more higher alcohols such as butanol (e.g., n -butanol and/or 2-butanol), hexanol, octanol, decanol, dodecanols, etc. as used herein, the "conversion" of an alpha hydrogen alcohol to a higher alcohol (HA) refers to an amount of the alpha hydrogen alcohol (AHA) consumed in the conversion reaction as represented by the formula:
where nAHA represents the molar flow rates of alpha hydrogen alcohol in the reactor effluent (eg, a product stream comprising the upper alcohol) and nAHA,0 represents the molar flow rate of alpha hydrogen alcohol at the reactor outlet. As used herein, the "higher alcohol selectivity" of conversion refers to an amount of the alpha hydrogen alcohol that is consumed in the conversion reaction that is converted formula: about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50%. In one embodiment, the higher alcohol conversion catalyst described herein may be capable of achieving a higher alcohol selectivity (SHA) in the reactive distillation process described herein of at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, or at least about 95%. The catalyst can be produced using a variety of techniques as described in more detail below.

[00127] Suitable conversion catalysts and combinations thereof are capable of converting at least a portion of alcohol (eg alpha hydrogen alcohol) in a feed stream to two or more highly valued products. For example, suitable conversion catalysts, and combinations thereof, are capable of producing one or more higher alcohols and/or ethyl acetate from alpha hydrogen alcohol (eg ethanol). Suitable conversion catalysts can comprise any catalyst capable of performing a dehydration, dehydrogenation and dimerization of the aldol condensation reaction, the dehydrogenation and dimerization reaction or a combination thereof and can be used alone or in combination with additional catalytic materials in the reactors. . In one embodiment, suitable conversion catalysts can generally comprise metals, oxides, or salts, or any combination thereof, of copper, barium, rethenium, rhodium, platinum, palladium, rhenium, silver, silicon, calcium, cadmium, zinc , zirconium, gold, thallium, magnesium, manganese, aluminum, chromium, nickel, iron, molybdenum, sodium, strontium, tin and mixtures thereof. In many cases, conversion of the catalyst material will be provided to a support material. Conversion catalysts can be treated with a carbonate (eg, sodium carbonate), reduced with water, and/or other suitable treatments before use.
[00128] Examples of suitable conversion catalysts include, but are not limited to, CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2, CuO/Al2O3, or any combination of the same. In one embodiment, CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2, CuO/Al2O3, or any combination thereof can be prepared via impregnation of a catalyst of oxide, such as, for example, by the impregnation techniques described herein and described in more detail below.
[00129] Examples of suitable conversion catalysts also include, but are not limited to, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO /BaO/SiO2, CuO/ZrO2/Al2O3/SiO2, CuO/Na2O/SiO2, CuO/MgO/Al2O3/SiO2, CuO/CeO2/MgO/Al2O3 or any combination thereof. In one embodiment, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/SiO2 , CuO/Na2O/SiO2, or any combination thereof, can be prepared by co-impregnating a silica catalyst support, such as, for example, by the co-impregnating techniques described herein and described in more detail below. In another embodiment, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/ SiO2, CuO/Na2O/SiO2, CuO/K20/SiO2, CuO/Rb2O/SiO2, CuO/Cs2O/SiO2, or any combination thereof can be prepared by sequentially impregnating a silica catalyst support such as, for example, by the sequential impregnation techniques described herein and described in more detail below.
[00130] Examples of suitable conversion catalysts also include, but are not limited to CuO/ZnO/Al2O3, CuO/Cr203/Al2O3, CuO/ZrO2/Al2O3, or any combination thereof. In one embodiment, CuO/ZnO/Al2O3, CuO/Cr203/Al2O3, CuO/ZrO2/Al2O3, or any combination thereof can be prepared by means of co-impregnation of an alumina support, such as, for example, by pellets. co-impregnation techniques described herein and described in more detail below.
[00131] Suitable conversion catalysts include Guerbet reaction catalysts, including but not limited to hydroxyapatite and solid base Guerbet reaction catalysts, solid base multicomponent oxide catalysts, zeolites with alkaline counterions, magnesium oxide, or any combination of the those capable of converting at least a portion of the alpha hydrogen alcohols (eg ethanol) into a feed stream to two or more higher valued products, the production of one or more higher alcohols (via a dehydration mechanism) and /or ethyl acetate (via a dehydrogenation mechanism) for example.
[00132] A conversion catalyst may comprise nickel or nickel oxide supported on alumina and a conversion catalyst may have a nickel weight loading between about 2% and about 60%. A conversion catalyst may comprise coprecipitated catalysts represented by the formula: M/MgO/Al2O3 where M represents palladium, rhodium, nickel, copper, or oxides thereof.
[00133] A conversion catalyst may comprise powders of copper oxide, lead, zinc, chromium, molybdenum, tungsten, manganese, lead, salts thereof and any combination thereof. In one embodiment, a conversion catalyst may comprise an alkali metal zeolite.
[00134] A conversion catalyst may comprise solid base catalysts and bifunctional solid base/acid catalyst. A conversion catalyst can comprise a hydroxyapatite represented by the formula Ca10(PO4)6(OH)2 wherein the ratio of calcium to phosphorus (Ca:P) is between about 1.5 and about 1.8 for non-stoichiometric hydroxyapatites . A conversion catalyst may comprise an apatite structure that satisfies the formula: Ma(M'Ob)CX2, where M represents calcium, strontium, magnesium, barium, lead, cadmium, iron, cobalt, nickel, or zinc, M' represents phosphorus, vanadium, arsenic, carbon or sulfur and X represents a fluorine, chlorine, bromine or a hydroxide. In one embodiment, a, b and c are total numbers that balance the valence requirements of M, M', and X. In another embodiment, a is 10, b is 3, and c is 6. In another embodiment, Ma (M'Ob)CX2 is a non-stoichiometric apatite and a is about 10, b is about 3, c is about 6, and the ratio of a to c (a:c) is between about 1.5 and about 1.8. A conversion catalyst can comprise a basic calcium and/or magnesium phosphate compound including calcium and/or magnesium phosphates, phosphate carbonates, pyrophosphates, or others. In one embodiment, a conversion catalyst may also comprise magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate (Mg3(PO4)2.8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate ( wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite (Ca10(PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), Ca2P2O7, hydrotalcite, talc, kaolin, sepiolite, or any combination thereof.
[00135] In certain embodiments, a conversion catalyst may include a catalyst support. The catalyst support stabilizes and supports the catalyst. The type of catalyst support used depends on the chosen catalyst and the reaction conditions. Suitable supports may include, but are not limited to, carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride, boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, zeolite, nanotubes of carbon, carbon fullerene and any combination thereof.
[00136] A conversion catalyst can be used in any of the conventional types or structures known in the art. They can be used in the form of extrudates, pills, globules, granules, broken fragments, or various special shapes. In one embodiment, consideration of using the conversion catalysts in the reactive distillation system and/or as a mass transfer surface within the distillation column can be taken into account when finishing a suitable shape. For example, conversion catalysts may be shaped similar to structured packaging material or suitable for insertion into structured packaging. When the hydrogenation catalyst is used with one or more secondary reactors, the catalyst can be arranged with a reaction zone and the feed can be passed through the entire mixed phase, liquid or steam and in an upward or downward flow or internal or external.
[00137] A conversion catalyst may typically have a range of metallic charges. In one embodiment, the conversion catalysts can have a barium oxide weight loading (i.e., percent by weight) between about 0.5% and about 80%, between about 10% and about 70 %, between about 20% and about 65%, between about 30% and about 60%, or about 40% and about 50%. In one embodiment, the conversion catalysts can have an aluminum oxide weight loading of between about 20% and about 60%, between about 30% and about 50%, or between about 40% and about 50%. In one embodiment, the conversion catalysts can have a zirconium dioxide weight loading of between about 20% and about 60%, or between about 30% and about 50%.
[00138] In one embodiment, the conversion catalysts may comprise CuO/Al2O3 disposed on a zirconium dioxide support. In this embodiment, the conversion catalysts can have a weight loading barium oxide between about 0.5% and about 80%, between about 10% and about 70%, between about 20% and about 65%, between about 30% and about 60%, or about 40% and about 50% and the alumina and zirconium dioxide can comprise the weight balance. In one embodiment, the conversion catalysts can comprise CuO/ZrO2 disposed on an alumina support. In this embodiment, the conversion catalysts can have a barium oxide weight loading between about 0.5% and about 80%, between about 10% and about 70%, between about 20% and about of 65%, between about 30% and about 60%, or about 40% and about 50% and the alumina and zirconium dioxide can comprise the weight balance.
[00139] In one embodiment, catalysts to co-produce higher alcohols and ethyl acetate from the ethanol described herein may be able to achieve a relatively high conversion and/or selectivity of the alpha hydrogen alcohols to one or more higher alcohols and ethyl acetate. As used herein, the "conversion" of the alcohol to alpha hydrogen of higher alcohols and ethyl acetate refers to the amount of the alpha hydrogen alcohols consumed in the conversion reaction as represented by the formula:
where nAHA represents the molar flow rates of the alpha hydrogen alcohols in the reactor effluent (eg, the product stream comprising the higher alcohols) and nAHA,0 represents the molar flow rate of the alpha hydrogen alcohols at the reactor inlet. As used herein, the "total selectivity" of conversion refers to the amount of the alpha hydrogen alcohol that is consumed in a conversion reaction that is converted to one or more higher alcohols and ethyl acetate and as represented by the formula:
where nAHA, nHA and nACH represents a molar flow rate of the alpha hydrogen alcohols, to one or more higher alcohols and acetaldehyde in the reactor effluent (eg, the product stream comprising the higher alcohols), respectively, and the remaining terms are the same as described above with respect to a conversion of alcohols to alpha hydrogen. Acetaldehyde is an intermediate in the reaction to make ethyl acetate (and possibly the reaction to make one or more of the higher alcohols) and is therefore included in the total selectivity calculation. In one embodiment, a conversion catalyst described herein may be capable of achieving the conversion of alpha hydrogen alcohols in the reactive distillation process described herein of at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50%. In one embodiment, a conversion catalyst described herein may be capable of achieving full selectivity (Stotal) in the reactive distillation process described herein of at least about 60%, at least about 70%, at least about 80 %, at least about 85%, at least about 90%, or at least about 95%.
[00140] It is understood that catalysts for the co-production of the higher alcohols and ethyl acetate may include a combination of one or more catalysts that convert the alpha hydrogen alcohols to pure or substantially pure higher alcohols with one or more catalysts that convert the alcohols from alpha hydrogen to pure and substantially pure ethyl acetate. Catalysts that convert alpha hydrogen alcohols to pure and substantially pure ethyl acetate include, but are not limited to, the catalysts described in U.S. Patent Publication No. 2013/0197266 entitled "Ethyl Acetate Production" by Gadewar, et al, which is incorporated herein by reference in its entirety. Various catalysts from U.S. Patent Publication No. 2013/0197266 suitable for use in the production of higher alcohols and/or ethyl acetate are further described in Examples 5-8 of the present application. The catalysts of Examples 5-8, however, are not intended to be a complete listing of all catalysts in U.S. Patent Publication No. 2013/0197266 suitable for use in the production processes of higher alcohols and/or ethyl acetate, systems and methods of the present application. Conversion catalysts can be produced using a variety of techniques as described in more detail below.
[00141] The hydrogenation catalyst can generally include a metal group VIII and/or a metal group VI. Examples of such a catalyst may include, but is not limited to, Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir and alloys, oxides (e.g., PtO2), or any combination thereof, alone or with promoters such as W, Mo, Au, Ag, Cr, Zn, Mn, Sn, B, P, Bi and alloys, oxides (for example, Cr2O3, Cu2Cr2O5), or any combination thereof. Other effective catalyst of hydrogenation materials include supported nickel or rhenium modified rethenium. In one embodiment, the hydrogenation catalyst also includes any of the supports described below, depending on the desired functionality of the catalyst. Hydrogenation catalysts can be prepared by methods known to those of ordinary skill in the art.
[00142] In one embodiment, the hydrogenation catalyst includes a supported group metal VIII catalyst and a metallic sponge material (for example, a nickel sponge catalyst such as Raney nickel). Raney Nickel provides an example of an activated nickel sponge catalyst suitable for use in this invention. In one embodiment, the hydrogenation reaction in the invention is carried out using a catalyst comprising a nickel-rhenium catalyst or a tungsten-modified catalyst. An example of a suitable catalyst for the hydrogenation reaction of the invention is a carbon-supported nickel-rhenium catalyst.
[00143] In one embodiment, a suitable Raney nickel catalyst can be prepared to treat an alloy of approximately equal amounts by weight of nickel and aluminum with an aqueous alkaline solution, for example, containing about 25% by weight of sodium hydroxide. An aluminum is selectively dissolved by the aqueous alkaline solution resulting in a sponge-formed material that comprises the most nickel with the smallest amounts of aluminum. The starting alloy includes promoter metals (eg molybdenum or chromium) in an amount such that 1 to 2% by weight remains in the formed sponge nickel catalyst. In another embodiment, the hydrogenation catalyst is prepared using a solution of rethenium(III) nitrosylnitrate or rethenium(III) chloride in water to impregnate a suitable support material. The solution is then dried to form a solid having a solids content of less than 1% by weight. The solid is then reduced at atmospheric pressure in a stream of hydrogen at 300°C. (not calcined) or 400°C. (calcined) in a rotary ball oven for 4 hours. After cooling and making the catalyst inert with nitrogen, 5% by volume of oxygen in nitrogen is passed over the catalyst for 2 hours.
[00144] In certain embodiments, the hydrogenation catalyst may include a catalyst support, which may be the same or different than a catalyst support used with a conversion catalyst. In one embodiment, any of the catalyst supports discussed herein can be used to support a hydrogenation catalyst. The hydrogenation catalyst can be used in any of the conventional types or structures known in the art. In one embodiment, any of the catalyst forms and/or types discussed herein with respect to a conversion catalyst can be used with the hydrogenation catalyst.
[00145] Any of the materials useful as catalysts, can be synthesized using a variety of methods. In one embodiment, the catalyst can be prepared by wet impregnation of a catalyst support. Using the wet impregnation technique, a metal salt (eg a metal nitrate, acetate, etc.) dissolved in a suitable solvent can be used to prepare the catalyst, however any soluble compound should be suitable. A sufficient amount of solvent must be used to fully dissolve the metal nitrate and properly wet the support. In one embodiment, copper nitrate and ethanol and/or water can be mixed in a sufficient amount such that the copper nitrate dissolves. Additional metal nitrates can also be added to provide a catalyst with additional components. The solute can then be combined with a suitable support material of the appropriate particle size. The mixture can then be refluxed at a temperature of approximately 100°C for approximately several hours (eg, three to five hours) and then allowed to dry at a temperature of approximately 110°C. The dried material can then be heated to 200°C to at least partially decompose the nitrates to the corresponding oxides and then the materials can be calcined at about 400°C to about 600°C at a heating rate of about one to ten°C/min in a period of about 2 to about 10 hours to completely remove the NOX component. The amount of metal nitrate used in the wet impregnation technique can be adjusted to achieve a desired final metal weight loading of the catalyst support.
[00146] When multiple components are used to provide a catalyst disposed on a support, each component can be added via the wet impregnation technique. Appropriate salts can be dissolved and impregnated onto a support in a co-impregnation process or a sequential process. In a co-impregnation process, metered amounts of the appropriate plurality of metal salts can be dissolved in a suitable solvent and used to wet the desired catalyst support. The impregnated support can then be dried and calcined to provide a final catalyst with a desired weight loading. In the sequential impregnation process, one or more measured amounts of the salts can be dissolved in a suitable solvent and used to wet the desired catalyst support. The impregnated support can be dried and calcined. The resulting material can then be wetted with one or more additional salts which are dissolved in a suitable solvent. The resulting material can then be dried and calcined again. This process can be repeated to provide a final catalyst material with a desired loading of each component. In one embodiment, a single metal can be added with each cycle. The order in which metals are added in the sequential process can be varied. Various weight bearing metals can be achieved through the wet impregnation technique. In one embodiment, the wet impregnation technique can be used to provide a catalyst having a copper weight loading ranging from about 0.5% to about 50%, with one or more additional components having a loading of weight between about 0.1% and about 40% each.
[00147] Catalysts can also be prepared by means of a co-precipitation technique. In this technique, a measured amount of one or more appropriate metal nitrates are dissolved in deionized water. The total metal concentration can vary and can generally be between about 0.01M and about 3M. The metal nitrate solution can then be precipitated by adding dropwise the solution to an equal stirred volume of a hydroxide solution of sodium at room temperature. Sodium hydroxide solution can generally have a concentration of about 4M, until other concentrations may also be used as would be known to one of skill in the art with the benefit of this discovery. In some embodiments, the solutions can be combined in the opposite order. For example, the metal salt solution can be prepared and added (for example, to the added drops) to a basic solution such as sodium hydroxide solution. The order of addition (eg metal salt solution to basic solution or basic solution to metal salt solution) can affect the composition of the precipitate formed during the precipitation process.
[00148] After addition of the metal nitrate solution or vice versa, the suspension can then be stirred for a period of about 1 to about 24 hours. The resulting suspension can then be filtered and washed with deionized water. The filtered solids can be dried overnight, for example, at a temperature of about 110°C and then the materials can optionally be calcined at about 220°C to about 500°C at a heating rate of about one to ten °C/min. The resulting mixed metal oxide can then be processed to a desired particle size. For example, the resulting mixed metal oxide can be compressed to a desired shape, crushed and then sieved to recover a catalyst material having a particle size in a desired range. Catalysts prepared using a co-precipitation technique may have higher metal loadings than catalysts prepared using the wet impregnation technique.
[00149] Catalysts prepared via the co-precipitation technique can be used in the prepared form and/or a catalyst binder can be added to impart additional mechanical strength. In one embodiment, the prepared catalyst can be ground into a fine powder and then stirred into a colloidal suspension (eg a colloidal suspension of silica and/or alumina) in an organic and/or aqueous solution. The resulting suspension can be stirred while being heated and allowed to evaporate to dryness. Heating can take place at around 80°C to around 130°C. The resulting solid can then be processed to a desired particle size. For example, the resulting solid can be extruded or compressed to a desired shape, crushed and then sieved to recover a catalyst material having a particle size in a desired range. Alternatively, the colloidal suspension can be added to 4M sodium hydroxide precipitation solution prior to addition of the metal nitrate solution in the coprecipitation technique. Other metal salts such as acetate chlorides, sulfates and others can be used in place of metal nitrates.
[00150] Various metal weight loadings can be achieved through the co-precipitation technique. In one embodiment, the co-precipitation technique can be used to provide a catalyst having a copper weight loading ranging from about 2% to about 80%, with one or more additional components having a weight loading of between about about 2% and about 40%.
[00151] The catalyst resulting from the wet impregnation technique and/or the co-precipitation technique can still be treated before use in the reactive distillation system described herein. In one embodiment, the catalyst can be treated with a basic solution such as a sodium carbonate solution or a dilute sodium hydroxide solution for a period of time to improve the selectivity of the catalyst. In this process, the catalyst may be saturated in an aqueous solution of sodium carbonate for a period of time ranging from about 1 hour to about 48 hours, or alternatively about 2 hours to about 24 hours. In one embodiment, the sodium carbonate solution can have a concentration of about 0.2M. The catalyst can then be filtered and allowed to dry at about room temperature. In one embodiment, the sodium carbonate can comprise from about 0.2 to about 3.0 percent by weight of the catalyst after being contacted with the sodium carbonate solution.
[00152] In another treatment process, the catalyst may be reduced with hydrogen before use. In this embodiment, the catalyst may be heated and contacted with hydrogen, which may be flowing over the catalyst, for a period of time sufficient to reduce the catalyst to a desired degree. In one embodiment, the catalyst may be contacted with hydrogen at a temperature from about 150°C to about 240°C. The hydrogen treatment can be carried out in combination with the soda ash treatment and can be carried out before and/or after the soda ash treatment. Without intending to be bound by theory, it is believed that hydrogen production during the dehydrogenation and dimerization reaction within the process can result in contact between a conversion catalyst and a stream of hydrogen sufficient to at least partially reduce the catalyst. Thus, the process described herein may have the potential for in-situ reduction of the catalyst during use. This can result in an initial breakdown period where catalyst conversion and selectivity may change before reaching a fixed-state conversion and selectivity. This in-situ reduction can be taken into account when considering the degree to which a catalyst should be pre-reduced with hydrogen.
[00153] In some embodiments, the catalyst used to produce one or more higher alcohols and/or ethyl acetate comprises a multi-component catalyst: a first dehydrogenation of the catalyst component and a second solid base catalyst component. While not intended to be bound by theory, it is believed that catalyst component dehydrogenation can catalyze reaction equations 2, 4 and 5 shown above and solid base catalyst component can catalyze reaction 4 shown above. The first component of the multi-component catalyst may comprise any of the elements of the catalysts described herein with respect to hydrogenation catalysts. The second component of the multi-component catalyst may comprise any of the elements of the catalysts described herein with respect to catalysts for producing one or more higher alcohols and/or any of the elements of the catalysts described herein with respect to catalysts for producing higher alcohols and ethyl acetate .
[00154] The relative amount of each of the first and second components can be varied in the multi-component catalyst to achieve the desired dehydrogenation/hydrogenation performance. In one embodiment, the amount of the first catalyst component can generally be less than about 30% by volume, less than about 25% by volume, less than about 20% by volume, less than about 15% by volume, less than about 10% by volume, or less than about 5% by volume. The amount of the first catalyst component can be greater than about 0.1% by volume, greater than about 1% by volume, greater than about 2% by volume, greater than about 3% by volume, greater than about 4% by volume, or greater than about 5% by volume. In one embodiment, the ratio of the volume of the first catalyst component to the volume of the second catalyst component can range from about 1:2 to about 1:100, from about 1:5 to about 1:90, or from about 1:10 to about 1:80.
[00155] In one embodiment, optional components such as binders and/or supports may also be present in the multi-component catalyst. The multi-component catalyst can be used in any of the conventional types or structures known in the art. They can be used in the form of extrudates, pills, globules, granules, broken fragments or various special shapes. In one embodiment, consideration of the use of the multi-component catalyst in the reactive distillation system and/or as a mass transfer surface within the distillation column can be taken into account when finishing a suitable shape. For example, the multi-component catalyst may be shaped similar to structured packaging material or suitable for insertion into structured packaging. In some embodiments, the catalyst can comprise a particular material that is dispersed in the reactants.
In some embodiments, the first catalyst component that catalyzes the hydrogenation-dehydrogenation should be any common hydrogenation catalyst for example Cu, Pd, Pt, Cr2O3, PtO2, and/or Cu2Cr2O5 (for example a Lazier catalyst) . Copper can be beneficial because of its lower cost and low by-product formation. In some embodiments, the second catalyst component of the multi-component catalyst may be one or more of MgO, Mg(OH)2, magnesium carbonates and calcium phosphates (e.g. Ca5(OH)(PO4)3, Ca2P2O7 and others calcium phosphates), natural or synthetic layered double hydroxide minerals such as hydrotalcite, kaolinite as well as the products of their interaction with alkaline earth oxides and hydroxides such as MgO, Mg(OH)2, CaO, Ca(OH)2 or its carbonates at high temperatures. Strontium and barium oxides, hydroxides and phosphates can also potentially be used in the process as solid base components.
[00157] The activity of the second component of the multicomponent catalyst was observed depending on the method of preparation. The multi-component catalyst can be prepared by any of the methods described herein to prepare a catalyst, including, but not limited to, physically mixing into two components, sol-gel co-precipitation, or loading the dehydrogenation catalyst onto the base catalyst component by impregnation. . Each of these methods has been observed to lead to the creation of the active catalyst. Physical mixing can be beneficial due to its simplicity, while an impregnation process results in the highest performance.
[00158] In one embodiment, the second catalyst component of the multi-component catalyst may comprise MgO. As illustrated in the examples accompanying its description, the activity of a catalyst comprising MgO has been observed to vary depending on its source, method of preparation and pretreatment. For example, purchased MgO was observed to have conversions less than about 5%, high surface area MgO (available from Nanoscale Materials Inc. of Manhattan, Kansas) was observed to have conversions up to about 26%, and MgO made from hydroxide decomposition and carbonate as described herein was observed to have conversions up to about 65%. Consequently, the present application describes the use of reactive distillation for the production of one or more higher alcohols from one or more alpha hydrogen alcohols, where higher alcohols are the primary reaction production. The present application describes the use of Guerbet reaction catalysts and other catalysts in a reactive distillation process to produce higher alcohols from alpha hydrogen alcohols. The present application also describes the production of higher alcohols and/or ethyl acetate from alpha hydrogen alcohols in a simple reactor. The present application describes the use of reactive distillation for the production of ethyl acetate and/or higher alcohols. Still further, the present application describes the use of supported catalysts, particularly CuO/ZrO2 supported on Al2O3 and CuO/Al2O3 supported on ZrO2, for the production of ethyl acetate and/or the higher alcohols. EXAMPLES
[00159] In general, the discovery described the following examples given as particular embodiments of the discovery and to demonstrate the practice and advantages of these. It is understood that the examples are given by way of illustration and are not intended to limit the specification or claims in any way. EXAMPLES 1-4
[00160] Examples 1-4 report the catalysts useful for the production of butanol, the production of butanol and/or ethyl acetate or a combination thereof in various systems and methods described in the present application. EXAMPLE 1 Preparation of Wet Impregnation Catalyst
[00161] The catalysts CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2 and CuO/Al2O3 were prepared by impregnation of an oxide catalyst support. In a typical co-impregnation, a measured amount of Cu(NO3^2.5H2O is dissolved in an appropriate amount of deionized water to fill the pore volume of the support. The solution is added to the support and stirred until the liquid is fully absorbed. impregnated substrate is then air-dried at 110°C, followed by calcination in air at 400 to 600°C for 2 to 10 hours.The amount of CII(NO3H2.5H20) can be adjusted to achieve a desired final Cu weight loading Typical Cu loadings are between 0.5 and 50% by weight EXAMPLE 2 Preparation of co-impregnation catalyst and sequential impregnation
[00162] The catalysts CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/SiO2 and CuO /Na2O/SiO2 were prepared by co-impregnation and sequential impregnation of a silica catalyst support. In a typical co-impregnation, the measured amounts of CuN(Oj-2.5l I2O and MINOC^YI I2O (M = Zn, ZrO, Mg, Ca, Sr, Ca, Al or Na; X = 1, 2, 4; Y = 2-6) are dissolved in an appropriate amount of deionized water to fill the pore volume of the silica support. The solution is added to the silica support and stirred until well mixed. The impregnated silica is then air-dried at 110°C, followed by calcining in air at 400 - 600°C for 2 - 10 hours Typical catalyst loading ranges range from 1-50 wt% CuO and 2 to 40 wt% MiOj.
[00163] The catalysts CuO/ZnO/Al2O3, CuO/Cr203/Al2O3 and CuO/ZrO2/Al2O3 were prepared by means of co-impregnation of an alumina support. A sample in which Cu, Zr and Al oxides were supported on alumina (CuO/ZrO2/Al2O3/Al2O3) was also prepared. In a typical co-impregnation, measured amounts of CU(NC)3H2.5H2O and M(NO3)X^YH2O (M = Zn, ZrO, or Cr; X =1, 2, 3; Y = 6 or 9) are dissolved in an appropriate amount of deionized water to fill the pore volume of the alumina support. The solution is added to the alumina support and stirred until the liquid is completely absorbed. The impregnated alumina is then dried in air at 110°C, followed by calcination in air at 400 - 600°C for 2 - 10 hours. Typical catalyst loadings range from 1 to 50% by weight CuO and 2 to 40% by weight MiOj.
[00164] The CuO/MgO/Al2O3/SiO2 and CuO/MgO/Al2O3/Al2O3 catalysts were prepared by means of co-impregnation and sequential impregnation of a silica or alumina catalyst support. In a typical co-impregnation, measured amounts of Cu(NO3)2^2.5H2O and M(NO3)X^YH2O or M(CH3COO)X.YH2O (M = Mg, Al; X = 2, 4; Y = 2- 6) are dissolved in an appropriate amount of deionized water. The solution is added to the silica or alumina support slowly and gradually to achieve distribution of good solids on the support (wetting of the incipient). The impregnated silica or alumina is then dried in air at 110°C, followed by calcination in air at 400 - 600°C for 2 - 10 hours. Typical catalyst loadings range from 1-50% by weight CuO and 2 to 40% by weight MiOj. An example of the final product is 1.5% by weight of Cu, 13% by weight of MgO and 2% by weight of Al2O3 on silica or granulated alumina. EXAMPLE 3 Preparation of Coprecipitation Catalyst
[00165] The mixed metal oxide catalysts were prepared by means of co-precipitation from the nitrate solutions. In a typical co-precipitation synthesis, a measured amount of the appropriate metal nitrates (Cu, Zn, Zr, Al, Cr, Fe, Ni, Ba) are dissolved in deionized water (total metal concentration ranges from 0.5 to 3 M) . The metal-nitrate solution is then precipitated by the dropwise addition of an equal stirred volume of 4 M aqueous NaOH at room temperature. After adding all of the metal nitrate solution, a suspension is stirred for 12 to 24 hours to ensure complete precipitation of the metal oxides. The precipitated solid is then filtered and washed with excess deionized water. The solids are then dried overnight at 110°C, followed by calcining at 220 to 500°C. Catalysts prepared in this way have CuO loadings between 40 to 80% by weight. Loadings of other metal oxides range from 2 to 40% by weight.
[00166] A catalyst binder can be added to the mixed metal oxide to impart additional mechanical strength. The metal oxide catalyst is ground to a fine powder and then stirred into a colloidal suspension of silica or alumina in water. The resulting suspension is stirred while heating at 80 to 130°C to dryness. The resulting solid then can be extruded or compressed, crushed or sieved to appropriate particle sizes. An alternative is to add the colloidal silica or alumina suspension to the 4M NaOH precipitating solution prior to addition of the metal nitrate solution. Other metal salts including acetates and carbonates can be used in place of nitrates. EXAMPLE 4 Dehydration, Dehydrogenation and Dimerization of Ethanol
[00167] A portion of the catalysts prepared as described in Examples 1-3 were tested in the butanol synthesis reactions after being reduced in a stream of H2 at a temperature between 175 and 240°C. The catalytic performance in the liquid phase reactions was then determined in a batch reactor at 180 - 200°C and 20 - 31 atm. The reactor pressure was maintained above the ethanol vapor pressure at the operating temperature. 4 g of the catalyst was used in each reaction and the batch reactor was charged with 15 ml of ethanol.
[00168] Table 1 shows a conversion and selectivity of catalysts in the dehydration and dehydrogenation dimerization reaction conducted in a fixed bed reactor. The conversion (Xethanol), selectivity of butanol (Sbutanol) and total selectivity (Stotal) were calculated from the composition of the reactor effluent as
respectively, where nEtOH, nbuOH and nACH represents a molar flow rate of ethanol, butanol (eg n-butanol and/or 2-butanol) and acetaldehyde in the reactor effluent (eg the product stream comprising butanol), respectively and the remaining terms are the same as described above with respect to an ethanol conversion. Acetaldehyde is an intermediate in the reaction to make ethyl acetate (and possibly to the reaction to make butanols) and is therefore included in the total selectivity calculation. Table 1 Conversion and selectivity for selected catalysts in a batch reactor operating at 200°C and 33 atm after 4 hours of reaction time.

[00169] From examples 1 through 4 it can be seen that the high total selectivity to butanol and ethyl acetate can be linked using the conversion catalysts described in this. In particular, the preparations of CuO/Al2O3 in ZrO2 and CuO/ZrO2 in Al2O3 catalysts each can simultaneously produce ethyl acetate and butanol, reaching a total selectivity above 90% and reaching a butanol selectivity above 20%. Based on examples 1 to 4, it can also be seen that a high total selectivity to butanol and ethyl acetate using the conversion catalysts described herein should be able to use the system of the embodiments as illustrated in the figures of the present description. EXAMPLES 5-8
[00170] Examples 5-8 relate to catalysts useful for the production of ethyl acetate in various systems and methods for the co-production of butanol and ethyl acetate described in the present application. Additional information regarding preparation of the catalysts described in Examples 5-8 can be seen in U.S. Patent Application No. 13/363,858, which is incorporated by reference herein in its entirety. EXAMPLE 5 Preparation of Wet Impregnation Catalyst
[00171] Various catalysts including CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2, CuO/ZnO/Al2O3, CuO/Cr203/BaO, CuO/Cr203 and CuO/Al2O3 were prepared by impregnating the corresponding oxide catalyst support. The preparation involved dissolving 4 grams (g) of CII(N(')3H2.5H2O) in 30 ml of deionized water, which was then added to 30 g of the appropriate oxide support and stirred until well mixed. The impregnated support was then dried in air at 110°C, followed by calcination in air at 450°C. The amount of CU(NO3^2.5H2O) was adjusted to achieve a Cu loading of desired final weight. Sufficient water was used to wet the total oxide support. Copper loadings between 0.5% and 20% by weight were EXAMPLE 6 Preparation of co-impregnation catalyst and sequential impregnation
[00172] Several catalysts including CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2 and CuO/Na2O/SiO2 were prepared by intermediate co-impregnation and sequential impregnation of a silica catalyst support. For the co-impregnation, measured amounts of CII(NO3H2,5H2O and M(NO3)X^YH2O (M = Zn, ZrO, Mg, Ca, Sr, Ca, or Na; X = 1, 2, 4; Y = 2- 6) were dissolved in deionized water.The solution was added to the silica support and stirred until well mixed.The impregnated silica was dried in air at 110°C, followed by calcination in air at 450°C.
[00173] For sequential impregnation, the measured amount of M(NO3)x. YH2O (M = Mg, Ca, Sr, Ca, or Na; X = 1 or 2; Y = 2-6) was dissolved in deionized water. The solution was then added to the silica support and mixed well. The silica was dried at 110°C and then calcined at 450°C in air. This procedure was then repeated using CU(NO3^2.5H2O in place of the first metal nitrate. Copper loadings between 0.5% and 20% by weight and a metal loading addition between 0.1% and 10% by weight were achieved EXAMPLE 7 Preparation of coprecipitation catalyst
[00174] The mixed metal oxide catalysts were prepared by means of co-precipitation from the nitrate solutions. In coprecipitation synthesis, the measured amount of the appropriate metal nitrate (Cu, Zn, Zr, Al, Cr, Fe, Ni, Ba, or any combination thereof) was dissolved in deionized water (total metal concentration ranges from 1 - 3 M). The metal-nitrate solution was then precipitated by the dropwise addition of an equal stirred volume of 4 M aqueous NaOH at room temperature. After addition of all the metal nitrate solution, the suspension was stirred for an additional 12 to 24 hours to ensure complete precipitation of the metals. The precipitated solid was then filtered and washed with excess deionized water. The solids were then dried overnight at 110°C. The resulting mixed metal oxide was then compressed, crushed or sieved to recover a catalyst with particle sizes between 450 and 850 µm. Catalysts prepared in this way have barium oxide loadings of between 40% and 80% by weight. The loadings of other metal oxides ranged from 2% to 40% by weight.
[00175] In addition to the catalysts prepared above, several catalysts were prepared through co-precipitation and then a binder was incorporated. The catalyst binder was added to the mixed metal oxide prepared as described above by first grinding the mixed metal oxide into a fine powder and then stirred into a colloidal suspension of silica or alumina in water. The resulting suspension was stirred while heating to 80-130°C for dryness. The resulting solid was then compressed, crushed or sieved to the appropriate particle sizes. EXAMPLE 8 Dehydrogenating Ethanol Dimerization
[00176] A portion of the catalysts prepared as described in Examples 5 to 7 were treated with a Na2CO3 solution by saturating the catalyst in a 0.2M aqueous solution of Na2CO3 for 2 - 24 hrs. The catalyst was then filtered and allowed to air dry at room temperature. Another portion of the catalysts prepared as described in Examples 3 to 5 were reduced in a hydrogen environment at 175 - 240°C for a period of 4 - 12 hours. These catalysts were then tested in ethanol dehydrogenation reactions. The conversion and selectivity for the gas phase reactions were determined from use in a fixed bed reactor operating at 190 - 240°C and 1 - 24 atm. Pure ethanol was fed to the reactor with a weighted hourly space velocity (WHSV) between 0.1 - 1.5 hr-1. The conversion and selectivity for the liquid and vapor/mixed liquid phase reactions were determined in the fixed bed reactor, operating at 190 - 240°C and at pressures above 25 atm. The liquid phase reactions were also conducted in a batch reactor at 180 - 200°C and 20 - 31 atm (the reactor pressure was maintained above the vapor pressure of ethanol at operating temperature).
[00177] Table 2 shows a conversion and selectivity of catalysts in a dehydrogenative dimerization reaction conducted in a fixed bed reactor. The conversion of ethanol (Xethanol) and "selectivity ethyl acetate" (Ethyl SaCetate) were calculated from the reactor effluent composition as
where FEtOH, FEtOAC and FACH represent the molar flow rates of ethanol, ethyl acetate and acetaldehyde in the reactor effluent, respectively, and FEtOH,0 represents the molar flow rate of ethanol at the reactor inlet. Acetaldehyde is a reaction intermediate and thus was included in the selectivity calculation. As used herein, the conversion selectivity of ethyl acetate refers to the amount of ethanol that is consumed in a conversion reaction that is converted to ethyl acetate. Table 2 Conversion and Selectivity for selected catalysts in a fixed bed reactor at 220°C and 1 atm Coprecipitation Catalysts

EXAMPLE 9 Conversion of ethanol to n-butanol using a Ca-pyrophosphate/Cu catalyst
[00178] A catalyst was prepared by mixing 8 grams of Ca2P2O7 with 0.2 g of CuO as powders. The catalyst was treated with hydrogen at 220°C. The catalyst (8 grams of catalyst) was contacted with ethanol at a flow rate of 0.04 ml/min at 260°C in the presence of 15.4 ml/min. hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 15% and the resulting selectivities are listed in Table 3. Table 3 Selectivities for example 9 selectivity, % by compound weight

EXAMPLE 10 Conversion of Ethanol to n-Butanol Using a Nanoparticulate MgO/Cu Catalyst.
[00179] A catalyst was prepared by mixing 8 grams of nanoparticulate nanoactive MgO (originated from Nanoscale Materials Corp. of Manhattan, Kansas) with 0.2 grams of CuO as powders. The catalyst was treated with hydrogen at 220°C. The catalyst (8 grams of catalyst) was contacted with ethanol at a flow rate of 0.04 ml/min at 300°C in the presence of 15.4 ml/min. hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 26% and the resulting selectivities are listed in Table 4. Table 4 Selectivities for example 10
EXAMPLE 11
[00180] Conversion of ethanol to n-butanol using synthetic Hydrotalcite/Cu catalyst
[00181] A catalyst was prepared by mixing 8 grams of synthetic hydrotalcite with 0.2 grams of CuO as powders. The catalyst was treated with hydrogen at 220°C. The catalyst (8 grams of catalyst) was contacted with ethanol at a flow rate of 0.04 ml/min at 260°C in the presence of 15.4 ml/min hydrogen co-feed. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 2% and the resulting selectivities are listed in Table 5. Table 5 Selectivities for example 11
EXAMPLE 12 Conversion of Ethanol to n-Butanol Using a Mg(OH)2/Cu Catalyst
[00182] A catalyst was prepared by mixing 9 grams of Mg(OH)2 with 0.5 grams of CuO as powders. The catalyst was treated with hydrogen at 220°C. The catalyst (8 grams of catalyst) was contacted with ethanol at a flow rate of 0.04 ml/min at 300°C without hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 64% and the resulting selectivities are listed in Table 6. Table 6 Selectivity for example 12

EXAMPLE 13
[00183] Conversion of ethanol to n-butanol using a synthetic hydrotalcite/Cu catalyst treated by Ca(OH)2
The catalyst was prepared by mixing 9 grams of synthetic hydrotalcite treated by Ca hydroxide with 0.6 grams of CuO as powders. Ca hydroxide treated hydrotalcite was prepared by mixing a slurry of 3 grams of Ca(OH)2 in 30 ml of water with 20 grams of synthetic hydrotalcite. The mixture was then heated to dryness followed by heating at 300°C for 2 hours. The catalyst was treated with hydrogen at 220°C.
[00185] The catalyst (8 grams of catalyst) was placed in contact with ethanol at a flow rate of 0.04 ml/min at 300°C without a hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 58% and the resulting selectivities are listed in Table 7. Table 7 Selectivity for example 13
EXAMPLE 14 Conversion of ethanol to n-butanol using a MgO (from basic magnesium carbonate)/Cu catalyst
[00186] The catalyst was prepared by mixing 9 grams of MgO prepared from basic Mg carbonate (available from Fisher Scientific of Waltham, MA) with 1 gram of CuO as powders. MgO was prepared by heating commercially available MgCO3.Mg(OH)2 to 450°C at a heating rate of about 1°C/min. The mixture was kept at 450°C for 2 hours. The mixed MgO and CuO catalyst was treated with hydrogen at 220°C.
[00187] The catalyst (8 grams of catalyst) was contacted with ethanol at a flow rate of 0.04 ml/min at 260°C without a hydrogen co-feed. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 52% and the resulting selectivities are listed in Table 8. Table 8 Selectivity for example 14
EXAMPLE 15 Conversion of ethanol to n-butanol using a MgO (from magnesium hydroxide)/Cu catalyst
[00188] The catalyst was prepared by mixing 9 grams of MgO prepared from Mg hydroxide (available from Fisher scientific of Waltham, MA) with 1 gram of CuO as powders. MgO was prepared by heating Mg(OH)2 in an open crucible to 450°C at a heating rate of about 1°C/min. Mg(OH)2 was kept at 450°C for about 2 hours. The mixed MgO and CuO catalyst was treated with hydrogen at 220°C.
[00189] The catalyst (8 grams of catalyst) was placed in contact with ethanol at a flow rate of 0.04 ml/min at 300°C without a hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated to be about 56% and the resulting selectivities are listed in Table 9. Table 9 Selectivity for example 15
EXAMPLE 16 Conversion of Ethanol to n-Butanol Using a MgO (from Magnesium Hydroxide)/Cu Catalyst Charged Through a Cu Salt Precursor
[00190] The catalyst was prepared gradually by mixing 10 grams of MgO prepared from Mg hydroxide (available from Fisher scientific of Waltham, MA) with 1.5 grams of Cu acetate hydrate as an ethanol solution. Once all the salt was transferred and the ethanol was evaporated, the material was heated to 415°C to generate the final catalyst. The MgO used in the mixture was prepared by heating Mg(OH)2 in a crucible to 450°C at a heating rate of about 1°C/min and holding the Mg(OH)2 at 450°C for 2 hours . The mixed catalyst was treated with hydrogen at 220°C.
[00191] The catalyst (8 grams of catalyst) was placed in contact with ethanol at a flow rate of 0.04 ml/min at 260°C without a hydrogen co-feeding. The reaction was carried out for 4 hours. The observed conversion was calculated at about 55% and the resulting selectivities are listed in Table 10. Table 10 Selectivity for example 16
EXAMPLE 17 Direct Synthesis of Higher Alcohols from Ethanol
[00192] The catalysts were tested for higher alcohol synthesis reactions in a fixed bed reactor operating at about 200 - 300°C and about 1 - 35 atm. The catalysts were reduced in a stream of H2 at a temperature between 175°C and 240°C before usp in the reactions.
[00193] Table 11 shows the composition of the reactor effluent using two different supported catalysts at different temperatures. The first catalyst was a mixture of CuO and MgO co-impregnated on a SiO2 support and the second was CuO, ZrO2 and Al2O3 co-impregnated on an Al2O3 support. The reactor effluent composition shown in Table 11 resulted from the use of 5.0 g of catalyst with a 0.10 ml/min ethanol feed at 3.44 MPa (500 psig). As expected, increasing temperature also increases a conversion of ethanol to higher alcohols. Significant amounts of acetaldehyde and butyraldehyde were also observed, but no crotonaldehyde was observed in the reactor effluent. In Table 11, "hexanols" include both 1-hexanol and 2-ethyl butanol, and "octanols" include 1-octanol and 2-ethyl hexanol. Table 11

[00194] Figure 13 shows a typical product distribution from CuO/MgO on SiO2 catalyst. Including the acetaldehyde and butyraldehyde intermediates along with all of the product alcohols, the total reaction selectivity is above 85% (the percentage of total ethanol consumed that is converted to the desired product or reaction intermediates). Other reaction products include mostly esters such as ethyl acetate, butyl acetate and ethyl butyrate, although some 2-butanone and 2-butanol are also present in the reactor effluent. The product distribution using CuO/ZrO2/Al2O3 on the Al2O3 catalyst, shown in Figure 14, shows a similar breakdown of reaction by-products, except a significant amount of diethyl ether is produced on this catalyst. EXAMPLE 18 Direct Synthesis of Higher Alcohols from Ethanol
[00195] The catalyst was prepared by mixing 10.7 grams of Mg-acetate. 4H2O with 0.6 gram of Al(OH)(OAc)2 and 0.6 g of Cu-acetate hydrate. The solids were dissolved in 150 ml of deionized water with the addition of 10 ml of glacial acetic acid. The solution was loaded onto 15 g of Saint Gobain 61138 silica (A) or 15 g of WR Grace 2720 alumina (B). The result loaded supports were heated to 350 °C at 1 °C/min and held at 350 °C for 3 h. The resulting catalysts (5 grams of each catalyst) were contacted with ethanol at a flow rate of 0.1 ml/min at 260°C without hydrogen co-feeding at a pressure of 3.44 MPa (500 psig). The reaction was carried out for 2 hours. The conversion observed by (A) was calculated to be about 30% and the resulting selectivity is listed in Table 12. Table 12

[00196] When loaded onto WR Grace alumina the observed conversion was 31% with observed product distribution selectivity listed in Table 13. Table 13


[00197] Having numerous systems and method described herein, various embodiments may include, but are not limited to:
[00198] In a first embodiment, a reactive distillation method comprises introducing a feed stream to a reactive distillation column, wherein the feed stream comprises ethanol; contacting the feed stream with a catalyst in the reactive distillation column during a distillation, wherein the feed stream reacts in the presence of the catalyst to produce a reaction product comprising butanol and water; removing butanol during distillation from the reactive distillation column as an underflow; and removing water during distillation from the reactive distillation column as an overhead stream.
[00199] A second embodiment may include the reactive distillation method of the first embodiment, further comprising: contacting the lower stream with a hydrogenation catalyst and hydrogen to hydrogenate at least a portion of a contaminant in the lower streams; and separating a hydrogenated portion of contaminant from the bottom stream.
[00200] A third embodiment may include the reactive distillation method of the second embodiment, wherein the hydrogenation catalyst comprises a metal group VIII, a metal group VI, or any combination thereof.
[00201] A fourth embodiment may include the reactive distillation method of any one of the first and third embodiments, wherein the catalyst comprises a catalyst capable of performing a dehydration and dimerization reaction.
[00202] A fifth embodiment may include the reactive distillation method of any one of the first to fourth embodiments, wherein the catalyst comprises a Guerbet reaction catalyst, a solid-based multi-component oxide catalyst, a bifunctional catalyst solid acid/basic, a zeolite with alkaline counter ions, a magnesium oxide catalyst, an oxide powder catalyst, or any combination thereof
[00203] A sixth embodiment may include the reactive distillation method of any one of the first to fifth embodiments, wherein the catalyst comprises a hydroxyapatite Guebert reaction catalyst, a solid base Guebert reaction catalyst or a combination of them.
[00204] A seventh embodiment may include the reactive distillation method of any one of the first to sixth embodiments, wherein the catalyst comprises nickel, nickel oxide supported on alumina, or a combination thereof.
[00205] An eighth embodiment may include the reactive distillation method of the seventh embodiment, wherein the catalyst has a nickel weight loading of between about 2% and about 20% of the catalyst.
[00206] A ninth embodiment may include the reactive distillation method of any one of the first to eighth embodiments, wherein the catalyst comprises a catalyst component represented by the formula: M/MgO/Al2O3, wherein M represents palladium , rhodium, nickel, or copper or oxides thereof
[00207] A tenth embodiment may include the reactive distillation method of any one of the first to ninth embodiments, wherein the catalyst comprises a hydroxyapatite represented by the formula: Ca10(PO4)6(OH)2, wherein the calcium to phosphorus (Ca:P) ratio is between about 1.5 and about 1.8.
[00208] An eleventh embodiment may include the reactive distillation method of any one of the first to tenth embodiments, wherein the catalyst comprises an apatite structure satisfying the formula: Ma(M'Ob)cX2, in where M represents calcium, strontium, magnesium, barium, lead, cadmium, iron, cobalt, nickel, zinc or hydrogen, where M' represents phosphorus, vanadium, arsenic, carbon or sulfur, where X represents a fluorine, chlorine, bromine or hydroxide and where a is about 10, b is about 3, c is about 6, and the ratio of a to c is between about 1.5 and about 1.8.
The twelfth embodiment may include the reactive distillation method of any one of the first to eleventh embodiments, wherein the catalyst comprises a calcium phosphate, a calcium carbonate phosphate, a calcium pyrophosphate, a magnesium phosphate, a magnesium carbonate phosphate, a magnesium pyrophosphate or any combination thereof.
[00210] A thirteenth embodiment may include the reactive distillation method of any one of the first to the twelfth embodiments, wherein the catalyst comprises magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate (Mg3(PO4) 2^8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite (Ca10( PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite, or any combination thereof
[00211] A fourteenth embodiment may include the reactive distillation method of any one of the first to thirteenth embodiments, wherein the catalyst comprises at least one catalyst component selected from the group consisting of: copper, barium oxide , barium, barium oxide, rethenium, ruthenium oxide, rhodium, rhodium oxide, platinum, platinum oxide, palladium, palladium oxide, rhenium, rhenium oxide, silver, silver oxide, cadmium, cadmium oxide, zinc , zinc oxide, zirconium, zirconium oxide, gold, gold oxide, thallium, thallium oxide, magnesium, magnesium oxide, manganese, manganese oxide, aluminum, aluminum oxide, chromium, chromium oxide, nickel, oxide nickel, iron, iron oxide, molybdenum, molybdenum oxide, sodium, sodium oxide, sodium carbonate, strontium, strontium oxidtalium, thallium oxide and any mixture thereof.
[00212] A fifteenth embodiment may include the reactive distillation method of any one of the first to fourteenth embodiments, wherein the catalyst comprises a support, wherein the support comprises at least one support material selected from the group which consists of: carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride, boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, a zeolite, a carbon nanotube, carbon fullerene and any combination of them.
A sixteenth embodiment may include the reactive distillation method of any one of the first to fifteenth embodiments, wherein the catalyst comprises copper and wherein the catalyst has a copper weight charge of between about 0 .5% and about 80% of the catalyst.
[00214] A seventeenth embodiment may include the reactive distillation method of any one of the first to sixteenth embodiments, wherein the catalyst comprises sodium carbonate.
[00215] An eighteenth embodiment may include the reactive distillation method of any one of the first through seventeenth embodiments, wherein the catalyst is at least partially reduced in the presence of hydrogen.
[00216] A nineteenth embodiment may include the reactive distillation method of any one of the first to eighteenth embodiments, wherein the conversion of ethanol in the feed stream to butanol is at least about 10%.
[00217] A twentieth embodiment may include the reactive distillation method of any one of the first to tenth embodiments, wherein the selectivity of ethanol to butanol conversion is at least about 15%.
[00218] A twenty-first embodiment may include the reactive distillation method of any one of the first to twenty-first embodiments, wherein the catalyst comprises a multi-component catalyst.
[00219] A twenty-second embodiment may include the reactive distillation method of the twenty-first embodiment, wherein the multi-component catalyst comprises a first catalyst component and a second catalyst component, wherein the first catalyst component comprises a catalyst component of dehydrogenation and wherein the second catalyst component is configured to convert at least a portion of ethanol in the feed stream to the reaction product comprising butanol and water.
[00220] A twenty-third embodiment may include the reactive distillation method of the twenty-second embodiment, wherein the first catalyst component comprises less than about 30% by volume of the combined volume of the first catalyst component and the second component of the catalyst.
A twenty-fourth embodiment may include the reactive distillation method of the twenty-second or twenty-third embodiment, wherein the first catalyst component comprises Cu, Pd, Pt, Cr2O3, PtO2, Cu2Cr2O5, any salt thereof, or any oxide of it.
[00222] A twenty-fifth embodiment may include the reactive distillation method of any one of the twenty-second to twenty-fourth embodiments, wherein the second catalyst component comprises magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate ( Mg3(PO4^8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite ( Ca10(PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite, or any combination thereof
[00223] A twenty-sixth embodiment may include the reactive distillation method of any one of the first to twenty-fifth embodiments, further comprising: removing a by-stream from the reactive distillation column; contacting the side stream with a second catalyst, wherein the side stream reacts in the presence of the second catalyst to produce butanol; and reintroducing the butanol produced in the presence of the second catalyst into the reactive distillation column.
[00224] A twenty-seventh embodiment may include the reactive distillation method of the twenty-sixth embodiment, wherein the catalyst comprises a butanol conversion catalyst suitable for use with a feed of ethanol and water and the second catalyst comprises a butanol conversion catalyst suitable for use with a pure or substantially pure ethanol feed.
[00225] A twenty-eighth embodiment may include the reactive distillation method of the twenty-sixth embodiment, wherein the catalyst comprises a butanol conversion catalyst suitable for use with a feed of pure or substantially pure ethanol and the second catalyst comprises a butanol conversion catalyst suitable for use with an ethanol and water feed.
[00226] A twenty-ninth embodiment may include the reactive distillation method of any one of the twenty-sixth to twenty-eighth embodiments, further comprising: adjusting a sidestream flow rate to maximize butanol production.
[00227] A thirtieth embodiment may include the reactive distillation method of any one of the twenty-sixth to twenty-ninth embodiments, further comprising: adjusting the sidestream flow rate in response to a change in feed composition.
[00228] A thirty-first embodiment may include the reactive distillation method of any one of the first to thirtieth embodiments, wherein a liquid portion of the feed stream is reacted in the presence of the catalyst to produce a reaction product comprising butanol and water.
[00229] A thirty-second embodiment may include the reactive distillation method of any one of the first to thirty-first embodiments, further comprising introducing a second feed stream comprising hydrogen into the reactive distillation column.
[00230] In a thirty-third embodiment, a reactive distillation system comprises a reactive distillation column comprising: a catalyst located generally central in the column, an ethanol feed in fluid communication with the reactive distillation column and configured to passing the ethanol over the catalyst, wherein the catalyst is configured to convert at least a portion of the ethanol feed to butanol in the reactive distillation column; an upper product dewatering passage and a lower product butanol removing passage; a product separation system comprising an inlet configured to receive bottom product from the reactive distillation column, a butanol product removal passage, and an ethanol removal passage; and a recycling line connection of the ethanol removal passage from the product separation system and an inlet to the reactive distillation column.
[00231] A thirty-fourth embodiment may include the reactive distillation system of the thirty-fourth embodiment, which further comprises a hydrogenation catalyst positioned to contact a liquid product followed by passage through the catalyst.
[00232] A thirty-fifth embodiment may include the reactive distillation system of the thirty-third or thirty-fourth embodiment, wherein the product separation system further comprises at least one light product removal pass or a light product removal pass. removal of heavier product.
[00233] A thirty-sixth embodiment may include the reactive distillation system of the thirty-third embodiment, whereas the reactive distillation column comprises a batch reactor configured to contact a liquid ethanol feed with the catalyst and remove water during contacting the liquid ethanol feed with the catalyst.
[00234] A thirty-seventh embodiment may include the reactive distillation system of the thirty-third embodiment, whereas the reactive distillation column comprises a continuous stirred tank reactor (CSTR) configured to contact a liquid ethanol feed with the catalyst and removing water during contact of the liquid ethanol feed with the catalyst.
[00235] A thirty-eighth embodiment may include the reactive distillation method of any one of the thirty-third to the thirty-seventh embodiments, further comprising introducing a second feed stream comprising hydrogen into the reactive distillation column.
[00236] A thirty-ninth embodiment may include the reactive distillation method of any one of the thirty-third to the thirty-eighth embodiments, wherein the catalyst comprises a multi-component catalyst, wherein the multi-component catalyst comprises a first catalyst component and a second catalyst component, wherein the first catalyst component comprises a dehydrogenation catalyst component and wherein the second catalyst component is configured to convert at least a portion of ethanol in the feed stream into the reaction product comprising butanol and water.
[00237] In a fortieth embodiment, a reactive distillation method comprises introducing a feed stream to a reactive distillation column, wherein the feed stream comprises ethanol; contacting the feed stream with a catalyst in the reactive distillation column during a distillation, wherein the feed stream reacts in the presence of the catalyst to produce a reaction product comprising butanol and water; separating a lower stream during distillation from the reactive distillation column, the lower stream comprising butanol and ethanol; separating a recycle stream from the downstream, wherein the recycle stream comprises at least a portion of ethanol from the downstream; and recycling the recycle stream into the reactive distillation column.
[00238] A forty-first embodiment may include the reactive distillation method of the forty-first embodiment, further comprising introducing a second feed stream comprising hydrogen into the reactive distillation column.
[00239] In a forty-second embodiment, a reactive distillation method comprises introducing a first feed stream to a reactive distillation column, wherein the first feed stream comprises ethanol; contacting the feed stream with a catalyst in the reactive distillation column during a distillation, wherein the feed stream reacts in the presence of the catalyst to produce a reaction product comprising butanol, ethyl acetate, water and hydrogen; removing butanol and ethyl acetate during column distillation as a lower product stream; and removing water and hydrogen during column distillation as an upper product stream.
[00240] A forty-third embodiment may include the reactive distillation method of the forty-second embodiment, wherein the feed stream further comprises water.
[00241] A forty-fourth embodiment may include the reactive distillation method of the forty-second or forty-third embodiment, wherein a ratio of butanol to ethyl acetate in the bottom product stream is increased by increasing an ethanol ratio the water in the supply stream.
[00242] A forty-fifth embodiment may include the reactive distillation method of any one of the forty-second to forty-fourth embodiments, further comprising introducing a second feed stream comprising hydrogen into the reactive distillation column.
[00243] A forty-sixth embodiment may include the reactive distillation method of the forty-fifth embodiment, wherein a ratio of butanol to ethyl acetate in the lower product stream is decreased by increasing an ethanol to hydrogen ratio in the supply current.
[00244] A forty-seventh embodiment may include the reactive distillation method of any one of the forty-second to forty-sixth embodiments, further comprising introducing the lower product stream to a second distillation column to separate the ethyl acetate and of butanol.
[00245] A forty-eighth embodiment may include the reactive distillation method of any one of the forty-second to forty-seventh embodiments, further comprising: contacting the lower stream with a hydrogenation catalyst and hydrogen to hydrogenate at least a portion of a contaminant in the downstream and separating the hydrogenated portion of the contaminant from the downstream.
[00246] A forty-ninth embodiment may include the reactive distillation method of the forty-eighth embodiment, wherein the hydrogenation catalyst comprises a Group VIII metal, a Group VI metal, or any combination thereof.
[00247] A fiftieth embodiment may include the reactive distillation method of any one of the forty-second to forty-second embodiments, wherein the catalyst comprises a catalyst capable of performing dehydration and dimerization reaction, dehydrogenation and dimerization reaction or a combination of them.
[00248] A fifty-first embodiment may include the reactive distillation method of any one of the forty-second to fifty-fifty embodiments, wherein the catalyst comprises at least one catalyst component selected from the group consisting of: copper, barium oxide , barium, barium oxide, rethenium, ruthenium oxide, rhodium, rhodium oxide, platinum, platinum oxide, palladium, palladium oxide, rhenium, rhenium oxide, silver, silver oxide, cadmium, cadmium oxide, zinc , zinc oxide, zirconium, zirconium oxide, gold, gold oxide, thallium, thallium oxide, magnesium, magnesium oxide, manganese, manganese oxide, aluminum, aluminum oxide, chromium, chromium oxide, nickel, oxide nickel, iron, iron oxide, molybdenum, molybdenum oxide, sodium, sodium oxide, sodium carbonate, strontium, strontium oxidtalium, thallium oxide and any mixture thereof
[00249] A fifty-second embodiment may include the reactive distillation method of any one of the forty-second to fifty-first embodiments, wherein the catalyst comprises a support, wherein the support comprises at least one support material selected from group consisting of: carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, a zeolite, a carbon nanotube, carbon fullerene, and any combination of them.
[00250] A fifty-third embodiment may include the reactive distillation method of any one of the forty-second to fifty-second embodiments, wherein the catalyst comprises CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ ZrO2, CuO/SiO2-ZrO2, CuO/Al2O3, or any combination thereof
[00251] A fifty-fourth embodiment may include the reactive distillation method of any one of the forty-second to fifty-third embodiments, wherein the catalyst comprises CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/ SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/SiO2, CuO/Na2O/SiO2, or any combination thereof.
A fifty-fifth embodiment may include the reactive distillation method of any one of the forty-second to fifty-fourth embodiments, wherein the catalyst comprises CuO/ZnO/Al2O3, CuO/Cr2O3/Al2O3, CuO/ZrO2/ Al2O3, or any combination thereof
[00253] A fifty-sixth embodiment may include the reactive distillation method of any one of the forty-second to fifty-fifth embodiments, wherein the catalyst comprises copper and wherein the catalyst has a copper weight charge of between about about 0.5% and about 80% catalyst.
[00254] A fifty-seventh embodiment may include the reactive distillation method of any one of the forty-second to fifty-sixth embodiments, wherein the catalyst comprises barium oxide and alumina disposed on a zirconium dioxide support.
[00255] A fifty-eighth embodiment may include the reactive distillation method of any one of the forty-second to fifty-seventh embodiments, wherein the catalyst comprises barium oxide and zirconium dioxide disposed on an aluminum support.
A fifty-ninth embodiment may include the reactive distillation method of any one of the forty-second to fifty-eighth embodiments, wherein the selectivity of converting ethanol to butanol and ethyl acetate is at least about 90 % and the selectivity of ethanol to butanol conversion is at least about 20%.
[00257] A sixty-ninth embodiment may include the reactive distillation method of any one of the forty-second to fifty-ninth embodiments, wherein the catalyst comprises sodium carbonate.
[00258] A sixty-first embodiment may include the reactive distillation method of any one of the forty-second to sixty-first embodiments, wherein the catalyst is at least partially reduced in the presence of hydrogen.
[00259] A sixty-second embodiment may include the reactive distillation method of any one of the forty-second to sixty-first embodiments, wherein the catalyst comprises a multi-component catalyst.
A sixty-third embodiment may include the reactive distillation method of the sixty-second embodiment, wherein the multi-component catalyst comprises a first catalyst component and a second catalyst component, wherein the first catalyst component comprises a catalyst component of dehydrogenation and wherein the second catalyst component is configured to convert at least a portion of the ethanol in the feed stream into the reaction product comprising butanol and water.
[00261] A sixty-fourth embodiment may include the reactive distillation method of the sixty-second embodiment, wherein the first catalyst component comprises less than about 30% by volume of the combined volume of the first catalyst component and the second component of the catalyst.
A sixty-fifth embodiment may include the method of reactive distillation of the sixty-third or sixty-fourth embodiment, wherein the first catalyst component comprises Cu, Pd, Pt, Cr2O3, PtO2, Cu2Cr2O5, any salt thereof or any oxide of this.
[00263] A sixty-sixth embodiment may include the reactive distillation method of any one of the sixty-third to sixty-fifth embodiments, wherein the second catalyst component comprises magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate ( Mg3(PO4^8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite ( Ca10(PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite, or any combination thereof
[00264] A sixty-sixth embodiment may include the reactive distillation method of any one of the forty-second to sixty-sixth embodiments, further comprising: removing a side stream from the reactive distillation column and contacting the side stream with a second catalyst, wherein the side stream reacts in the presence of the second catalyst to produce butanol.
[00265] A sixty-eighth embodiment may include the reactive distillation method of the sixty-seventh embodiment, further comprising: adjusting a sidestream flow rate to achieve a desired lower stream composition.
[00266] A sixty-ninth embodiment may include the reactive distillation method of the sixty-eighth embodiment, wherein the adjustment comprises increasing the sidestream flow rate to increase the production of butanol relative to ethyl acetate.
[00267] A seventy-eighth embodiment may include the reactive distillation method of the sixty-eighth embodiment, wherein adjusting comprises decreasing the flow rate of the secondary current to decrease the production of butanol relative to ethyl acetate.
[00268] A seventy-first embodiment may include the reactive distillation method of any one of the forty-second to sixty-sixth embodiments, further comprising: removing a side stream from the reactive distillation column and contacting the side stream with a second catalyst, wherein the side stream reacts in the presence of the second catalyst to produce ethyl acetate.
[00269] A seventy-second embodiment may include the reactive distillation method of the seventy-first embodiment, further comprising: adjusting a sidestream flow rate to achieve a desired lower stream composition.
[00270] A seventy-third embodiment may include the reactive distillation method of the seventy-second embodiment, wherein the adjustment comprises increasing the sidestream flow rate to decrease the production of butanol relative to ethyl acetate.
[00271] A seventy-fourth embodiment may include the reactive distillation method of the seventy-second embodiment, wherein adjusting comprises decreasing the secondary current flow rate to increase the production of butanol relative to ethyl acetate.
A seventy-fifth embodiment may include the reactive distillation method of the seventy-second embodiment, wherein adjusting comprises cutting off the flow rate of the side stream to produce pure or substantially pure butanol.
[00273] A seventy-sixth embodiment may include the reactive distillation method of any one of the forty-second to seventy-fifth embodiments, wherein a liquid portion of the feed stream reacts in the presence of the catalyst to produce a reaction product that comprises butanol and water.
[00274] In a seventy-seventh embodiment, a reactive distillation system comprises: a feed stream comprising ethanol; a reactive distillation column comprising: a catalyst located generally centrally in the column, an ethanol feed in fluid communication with the reactive distillation column and configured to pass ethanol from the feed stream over the catalyst, a product water upper and hydrogen removal pass and a lower product butanol and ethyl acetate removal pass; a product separation system comprising an inlet configured to receive bottom product from the reactive distillation column, a butanol product removal passage and an ethyl acetate product removal passage.
A seventy-eighth embodiment may include the reactive distillation system of the seventy-seventh embodiment, which further comprises a lower ethanol recycling line connection in the ethanol removal passage of the product separation system and an inlet in the reactive distillation column.
[00276] A seventy-ninth embodiment may include the reactive distillation system of any one of the seventy-seventh or seventy-eighth embodiments, further comprising a separator and an upper ethanol recycling line, wherein the water of the higher product and the hydrogen removal passage connects the reactive distillation column to the separator and the upper ethanol recycle line connects the separator to an inlet in the reactive distillation column.
[00277] A eighty-ninth embodiment may include the reactive distillation system of any one of the seventy-seventh to seventy-ninth embodiments, further comprising a hydrogenation catalyst positioned to contact a liquid product following passage over the catalyst.
[00278] An eighty-first embodiment may include the reactive distillation system of any one of the seventy-seventh through eighty-first embodiments, wherein the product separation system further comprises at least one of the light product removal passages or a heavy product removal pass. An eighty-second embodiment may include the reactive distillation system of the seventy-seventh embodiment, and that reactive distillation column comprises a batch reactor configured to contact a liquid ethanol feed with the catalyst and remove water during contact with the feeding liquid ethanol with the catalyst.
[00279] An eighty-third embodiment may include the reactive distillation system of the seventy-seventh embodiment, and that the reactive distillation column comprises a continuous stirred tank reactor (CSTR) configured to contact a liquid ethanol feed with the catalyst and removing water during contact of the liquid ethanol feed with the catalyst.
An eighty-fourth embodiment may include the method of reactive distillation of any one of the seventy-seventh to eighty-third embodiments, further comprising introducing a second stream comprising hydrogen into the reactive distillation column.
[00281] In an eighty-fifth embodiment, a reactive distillation method comprises introducing a feed stream to a reactive distillation column, wherein the feed stream comprises ethanol; contacting the feed stream with a catalyst in the reactive distillation column during a distillation, wherein the feed stream reacts in the presence of the catalyst to produce a reaction product comprising butanol, ethyl acetate, water and hydrogen; separating the lower stream during distillation from the reactive distillation column, the lower stream comprising butanol and ethyl acetate; separating an upper stream during distillation from the reactive distillation column, the upper stream comprising water and ethanol; separating the recycle stream from an overhead stream, wherein the recycle stream comprises at least a portion of the ethanol from an overhead stream, and recycling the recycle stream into the reactive distillation column.
[00282] A eighty-sixth embodiment may include the reactive distillation method of the eighty-fifth embodiment, further comprising: separating at least one by-product from the recycle stream after separating the recycle stream from an overhead stream and before recycling the recycle stream into the reactive distillation column.
[00283] An eighty-seventh embodiment may include the method of reactive distillation of the eighty-fifth or eighty-sixth embodiment, further comprising: separating the lower stream into a product stream and the recycle stream and separating the product stream m a by-product stream and a butanol product stream.
[00284] An eighty-eighth embodiment may include the method of reactive distillation of any one of the eighty-fifth to eighty-seventh embodiments, further comprising introducing a second stream comprising hydrogen into the reactive distillation column.
[00285] An eighty-ninth embodiment may include the method of reactive distillation of any one of the eighty-fifth to the eighty-eighth embodiment, wherein the catalyst comprises a multi-component catalyst.
[00286] A ninety-ninth embodiment may include the reactive distillation method of the eighty-ninth embodiment, wherein the multi-component catalyst comprises a first catalyst component and a second catalyst component, wherein the first catalyst component comprises a dehydrogenation catalyst component and wherein the second catalyst component is configured to convert at least a portion of the ethanol in the feed stream to the reaction product comprising butanol and water.
[00287] A ninety-first embodiment may include the reactive distillation method of the ninety-first embodiment, wherein the first catalyst component comprises less than about 30% by volume of the combined volume of the first catalyst component and the second component of the catalyst.
[00288] A ninety-second embodiment may include the method of reactive distillation of the ninety-first or ninety-first embodiment, wherein the first catalyst component comprises Cu, Pd, Pt, Cr2O3, PtO2, Cu2Cr2O5, any salt thereof or any oxide of this.
[00289] A ninety-third embodiment may include the reactive distillation method of any one of the ninety to ninety-second embodiments, wherein the second catalyst component comprises magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate (Mg3 (PO4^8H2O), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite (Ca10 (PO4)6F2), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite or any combination thereof
[00290] In a ninety-fourth embodiment, a reactive distillation method comprises: introducing a feed stream to a reactive distillation column, wherein the feed stream comprises one or more alpha hydrogen alcohols; contacting the feed stream with one or more catalysts in the reactive distillation column during a distillation, wherein the feed stream reacts in the presence of the one or more catalysts to produce a reaction product comprising one or more higher alcohols and remove the alcohols during the distillation of the reactive distillation column as a bottom stream.
[00291] A ninety-fifth embodiment may include the method of the ninety-fourth embodiment, wherein the one or more alpha hydrogen alcohols comprise one or more of ethanol, propanol or butanol.
[00292] A ninety-sixth embodiment may include the method of the ninety-fourth embodiment, wherein the one or more alpha hydrogen alcohols comprise only ethanol.
[00293] A ninety-seventh embodiment may include the method of any one of the ninety-fourth to ninety-sixth embodiments, wherein the one or more higher alcohols comprises a C6-C13 alcohol.
[00294] A ninety-eighth embodiment may include the method of any one of the ninety-fourth to ninety-sixth embodiments, wherein the one or more higher alcohols comprise at least one alcohol selected from the group consisting of: 1-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-ethyl-2-hexanol, heptanol, decanol and dodecanols.
[00295] A ninety-ninth embodiment may include the reactive distillation method of any one of the ninety-fourth to ninety-eighth embodiments, wherein the catalyst comprises a Guerbet reaction catalyst, a multi-component oxide based catalyst solid, a solid acid/base bifunctional catalyst, a zeolite with alkaline counter ions, a magnesium oxide catalyst, an oxide powder catalyst, or any combination thereof.
A hundredth embodiment may include the reactive distillation method of any one of the ninety-fourth to ninety-ninth embodiments, wherein the catalyst comprises a dual-function catalyst.
[00297] A hundredth embodiment may include the reactive distillation method of any one of the ninety-fourth to one hundredth embodiments, wherein the catalyst comprises a Guebert reaction catalyst of hydroxyapatite, a Guebert reaction catalyst of solid foundation or a combination thereof.
[00298] A hundred-second embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundredth embodiment, wherein the catalyst comprises CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ ZrO2, CuO/SiO2-ZrO2 CuO/Al2O3, CuO/MgO, CuO/MgO/SiO2, CuO/MgO/Al2O3, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2 , CuO/SrO/SiO2, CuO/BaO/SiO2, CuO/ZrO2/Al2O3/SiO2 and CuO/Na2O/SiO2, CuO/ZnO/Al2O3, CuO/Cr203/Al2O3 and CuO/ZrO2/Al2O3, or any combination thereof .
[00299] A hundred-third embodiment may include the reactive distillation method of the hundred-second embodiment, wherein the catalyst has a copper weight charge of between about 0.5% and about 50% of the catalyst.
[00300] A hundred-fourth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundred-third embodiment, wherein the catalyst comprises a catalyst component represented by the formula: M/MgO/Al2O3, wherein M represents palladium, rhodium, platinum, silver, gold, nickel, or copper or oxides thereof.
[00301] A hundred-fifth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundredth-fourth embodiment, wherein the catalyst comprises a hydroxyapatite represented by the formula: Ca10(PO4)6(OH)2, wherein the ratio of calcium to phosphorus (Ca:P) is between about 1.5 and about 1.8.
[00302] A hundred-sixth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundredth-fifth embodiments, wherein the catalyst comprises an apatite structure satisfying the formula: Ma(M'Ob)CX2 , where M represents calcium, strontium, magnesium, barium, lead, cadmium, iron, cobalt, nickel, zinc or hydrogen, where M' represents phosphorus, vanadium, arsenic, carbon or sulfur, where X represents a fluorine, chlorine , bromine or hydroxide and where a is about 10, b is about 3, c is about 6, and the ratio of a to c is between about 1.5 and about 1.8.
[00303] A hundred-seventh embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundred-sixth embodiments, wherein the catalyst comprises a calcium phosphate, a calcium carbonate phosphate, a calcium pyrophosphate, a magnesium phosphate, a magnesium carbonate phosphate, a magnesium pyrophosphate or any combination thereof
[00304] A hundred-eighth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundred-seventh embodiments, wherein the catalyst comprises magnesium oxide, magnesium hydroxide, hydrated magnesium phosphate (Mg3(POiH8H2O) ), calcium oxide, calcium hydroxide, calcium fluoride, calcium silicate (wollastonite), calcium sulfate dihydrate (gypsum), lithium phosphate, aluminum phosphate, titanium dioxide, fluoroapatite (Ca10(PO4)6F2 ), tetracalcium phosphate (Ca4(PO4)2O), hydrotalcite, talc, kaolin, sepiolite, or any combination thereof
[00305] A hundred-ninth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundred-eighth embodiments, wherein the catalyst comprises at least one catalyst component selected from the group consisting of: copper, copper oxide. barium, barium, barium oxide, rethenium, ruthenium oxide, rhodium, rhodium oxide, platinum, platinum oxide, palladium, palladium oxide, rhenium, rhenium oxide, silver, silver oxide, cadmium, cadmium oxide, zinc, zinc oxide, zirconium, zirconium oxide, gold, gold oxide, thallium, thallium oxide, magnesium, magnesium oxide, manganese, manganese oxide, aluminum, aluminum oxide, chromium, chromium oxide, nickel, nickel oxide, iron, iron oxide, molybdenum, molybdenum oxide, sodium, sodium oxide, sodium carbonate, strontium, strontium oxidtalium, thallium oxide and any mixture thereof
[00306] A hundred-tenth embodiment may include the reactive distillation method of any one of the ninety-fourth to the hundred-ninth embodiments, wherein the catalyst comprises a multi-component catalyst.
[00307] A hundred and eleventh embodiment may include the reactive distillation method of the one hundred and tenth embodiments, wherein the multi-component catalyst comprises a first catalyst component and a second catalyst component, wherein the first catalyst component is configured to converting a portion of the ethanol in the feed stream to ethyl acetate and wherein the second catalyst component is configured to convert at least a portion of the ethanol in the feed stream to butanol and water.
[00308] A hundred and twelfth embodiment may include the method of reactive distillation of any one of the ninety-fourth to one hundred and eleventh embodiments, further comprising: removing a by-stream from the reactive distillation column; contacting the side stream with a secondary reactor catalyst, wherein the side stream reacts in the presence of the secondary reactor catalyst to produce a higher alcohol and reintroducing the higher alcohol produced in the presence of the secondary reactor catalyst into the reactive distillation column.
[00309] A hundred and thirteenth embodiments may include the reactive distillation method of any one of the ninety-fourth to the hundredth-twelfth embodiments, further comprising: adjusting a reactive distillation column pressure to increase higher alcohol production .
[00310] A one hundred and fourteenth embodiment may include the method of reactive distillation of any one of the ninety-fourth to one hundred and fourteenth embodiments, further comprising introducing a second stream comprising hydrogen into the reactive distillation column.
[00311] In a one hundred and fifteenth embodiment, a reactive distillation method comprises: introducing a feed stream to a reactive distillation column, wherein the feed stream comprises ethanol; contacting the feed stream with one or more catalysts during a distillation, wherein the feed stream reacts in the presence of the one or more catalysts to produce a reaction product comprising a C6-C13 alcohol and removing the C6-C13 alcohol during the distillation from the reactive distillation column as a bottom stream.
[00312] A one hundred and sixteenth embodiment may include the method of the one hundred and fifteenth embodiment, wherein the one or more catalysts are disposed in the reactive distillation column.
[00313] A one hundred seventeenth embodiment may include the method of the one hundred and fifteenth embodiment, wherein the one or more catalysts are disposed in a side reactor in fluid communication with the reactive distillation column.
[00314] A one hundred and eighteenth embodiment may include the reactive distillation method of the one hundred and seventeenth embodiment, further comprising: removing a by-stream from the reactive distillation column; contacting the side stream with a secondary reactor catalyst in the secondary reactor, wherein the side stream reacts in the presence of the secondary reactor catalyst to produce the C6-C13 alcohol and reintroduce the C6-C13 alcohol produced in the presence of the secondary reactor catalyst into the reactive distillation column.
[00315] A one hundred and nineteen embodiments may include the reactive distillation method of any one of the one hundred fifteenth to one hundred and eighteenth embodiments, further comprising: removing the bottom stream from the reactive distillation column, wherein the stream feed reacts in the presence of the one or more catalysts to produce a reaction product comprising C6-C13 alcohol and butanol and wherein the lower stream comprises C6-C13 alcohol and butanol; separate at least a portion of the C6-C13 alcohol from the C2-C5 alcohols and recycle the C2-C5 alcohols into the reactive distillation column.
[00316] A one hundred and twentieth embodiment may include the method of reactive distillation of any one of the one hundred fifteenth to one hundred and nineteenth embodiments, further comprising: adjusting a reactive distillation column pressure to increase the production of C6 alcohol -C13.
[00317] In a one hundred and twenty-first embodiment, the reactive distillation system comprises: a feed stream comprising an alpha hydrogen alcohol, where the alpha hydrogen alcohol is heavier than methanol; a reactive distillation column, and that the reactive distillation column comprises: one or more catalysts disposed within the reactive distillation column, an alcohol hydrogen feed configured to pass the feed stream comprising the alpha hydrogen alcohol over at least one portion of the one or more catalysts to produce a higher alcohol, wherein the one or more catalysts are configured to cause the alpha hydrogen alcohol to react in the presence of the one or more catalysts to produce the higher alcohol, and wherein the higher alcohol comprises an alcohol that is heavier than alpha hydrogen alcohol; a top product hydrogen removal pass and a bottom product top alcohol removal pass.
[00318] A hundred and twenty-second embodiment may include the system of the one hundred and twenty-first embodiment, further comprising: a secondary reactor in fluid communication with the reactive distillation column, wherein the secondary reactor comprises a second catalyst; an inlet in fluid communication with the secondary reactor and the reactive distillation column is configured to pass a fluid from the reactive distillation column over the second catalyst and an outlet in fluid communication with the secondary reactor and the reactive distillation column is configured to pass fluid from an outlet of the secondary reactor into the reactive distillation column.
[00319] A one hundred twenty-third embodiment may include the reactive distillation system of the one hundred twenty-second embodiment, wherein the inlet is connected to the reactive distillation column below the outlet.
[00320] A one hundred twenty-fourth embodiment may include the reactive distillation system of the one hundred twenty-third embodiment, wherein the fluid is a vapor.
[00321] A one hundred twenty-fifth embodiment may include the reactive distillation system of the one hundred twenty-second embodiment, wherein the inlet is connected to the reactive distillation column above the outlet.
[00322] A one hundred twenty-sixth embodiment may include the reactive distillation system of the one hundred twenty-second embodiment, wherein the fluid is a liquid.
[00323] A one hundred twenty-seventh embodiment may include the reactive distillation system of any one of the one hundred twenty-first to one hundred twenty-sixth embodiments, wherein the reactive distillation system further comprises: a hydrogen feed in communication of fluid with the reactive distillation column and configured to pass hydrogen over at least a portion of the one or more catalysts.
A one hundred twenty-eighth embodiment may include the reactive distillation system of any one of the one hundred twenty-first to one hundred twenty-seventh embodiments, wherein the alpha hydrogen alcohol feed comprises a C2-C5 alpha hydrogen alcohol.
[00325] A one hundred twenty-ninth embodiment may include the reactive distillation system of any one of the one hundred twenty-first to one hundred twenty-eighth embodiments, wherein the higher alcohol comprises a C6-C13 alcohol.
[00326] In a one hundred and thirtieth embodiment, a method of separating a mixed aqueous and organic phase stream, the method comprising: separating an input stream into an upper stream and a lower stream into a separation unit, wherein the inlet stream comprises water, butanol and an ester, the upper stream comprising water and the esters and the lower stream comprising butanol; passing a current over a decanter; generating, in the decanter, an aqueous phase comprising substantially all of the water and an organic phase comprising the esters; removing the aqueous phase from the decanter as an aqueous stream; removing the organic phase from the decanter as an organic stream; separating the organics stream into a product stream and a recycle stream, wherein the product stream comprises the esters and wherein the recycle stream comprises the water.
[00327] A hundred and thirty-first embodiment may include the method of the hundred and thirty-first embodiment, wherein the esters comprise ethyl butyrate.
[00328] A hundred-thirty-second embodiment may include the method of the hundred-thirty or the hundred-thirty-first embodiment, wherein the lower stream comprises butanol having a purity of at least about 90% butanol by weight.
[00329] A hundred-thirty-third embodiment may include the method of any one of the hundred-thirty to the hundred-thirty-second embodiments, wherein the separation unit comprises the distillation column.
[00330] A hundred-thirty-fourth embodiment may include the method of any one of the hundred-thirty to the hundred-thirty-third embodiments, further comprising: recycling the recycling stream into an input stream.
[00331] In a one hundred and thirty-fifth embodiment, a method of separating a mixed aqueous and organic phase stream, the method comprises: separating an input stream into an upper stream and a lower stream into a separation unit, wherein the inlet stream comprises water, a plurality of higher alcohols and an ester, wherein the upper stream comprises water the esters and a first portion of the plurality of higher alcohols, and wherein the lower stream comprises a second portion of the plurality of higher alcohols ; separating the lower stream into at least one product stream comprising a first higher alcohol from the first portion of the plurality of higher alcohols; passing a current over a decanter; generating, in the decanter, an aqueous phase comprising substantially all of the water and an organic phase comprising the esters and the second portion of the plurality of higher alcohols; removing the aqueous phase from the decanter as an aqueous stream; removing the organic phase from the decanter as an organic stream; separating the organics stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols.
A one hundred and thirty-sixth embodiment may include the method of the one hundred and thirty-fifth embodiment, wherein separating the lower stream into at least one product stream comprises: separating the lower stream into a first product stream comprising butanol and a second product stream comprising the remainder of the first portion of the plurality of higher alcohols.
A hundred and thirty-seventh embodiment may include the method of the hundred and thirty-fifth embodiment, wherein separating the lower stream into at least one product stream further comprising: separating the remainder of the first portion of the plurality of higher alcohols in a third product stream comprising hexanol.
[00334] A hundred and thirty-eighth embodiment may include the method of the hundred and thirty-fifth embodiment, wherein separating the organics stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of alcohols uppers comprises: separating the organics stream into a second upper stream comprising the esters and water and a second lower stream comprising the second portion of the plurality of higher alcohols.
[00335] A hundred and thirty-ninth embodiment may include the method of the hundred and thirty-eighth embodiment, wherein separating the organics stream into a first stream comprising the esters and a second stream comprising the second portion of the plurality of alcohols uppers which further comprises: passing the second upper stream to a second decanter; generating in the second decanter, a second aqueous phase comprising substantially all of the water in the stream of organics and a second organic phase comprising the esters; removing the second aqueous phase from the second decanter as a second aqueous stream; removing the second organic phase from the second decanter as a second organic stream; separating the second organic stream into a product stream ester comprising the esters.
[00336] A hundred and fortieth embodiment may include the method of the hundred and thirty-eighth embodiment, wherein separating the stream of organics into a first stream comprising the esters and a second stream comprising the second portion of the plurality of higher alcohols further comprising: separating the second lower stream into a third upper stream and a third lower stream, wherein the third upper stream comprises at least one higher alcohol from the second portion of the plurality of higher alcohols.
[00337] A hundred and forty-first embodiment may include the method of the hundred and forty-first embodiment, wherein separating the second lower stream into a third upper stream and a third lower stream occurs at a pressure greater than about 3 atmospheres.
[00338] A hundred and forty-second embodiment may include the method of any one of the one hundred thirty-fifth to one hundred forty-first embodiments, wherein the esters comprise one or more of ethyl acetate or ethyl butyrate.
[00339] In a hundred and forty-third embodiment, a method of separating an alcohol from ethyl acetate, the method comprises: adding water to an inlet stream to form a combined stream, wherein the inlet stream comprises an alcohol and ethyl acetate; distilling the combined stream to produce an upper stream and a lower stream, wherein the upper stream comprises water and ethyl acetate and the lower stream comprises a majority of alcohol; condensing the upper stream and decanting an aqueous phase stream from an organic phase stream, wherein the aqueous phase stream comprises a majority of the water in the upper stream and wherein the organic phase stream comprises a majority of the ethyl acetate in the stream higher.
In the foregoing debate and claims, the terms "including" and "comprising" are used in an open-ended manner, and as such, are to be interpreted to mean "including, but not limited to ...". At least one embodiment is described and variations, combinations and/or modifications of the embodiments and/or features of the embodiments made by a person having ordinary skill in the art are within the scope of the description. Alternative embodiments that result from combining, integrating and/or omitting the features of the embodiments are also within the scope of the description. Where numerical ranges or limitations are expressly stated, such express ranges and limitations are to be understood to include iterative ranges or limitations of similar magnitude that fall within expressly stated ranges or limitations (eg, from about 1 to about 10 includes, 2 , 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, when a numerical range with a lower limit, R1 and an upper limit, Ru, is described, any number that falls within the range is specifically described. In particular, the following numbers within the range are specifically described: R=R1+k*(Ru-R1), where k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, this is, k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent percent, 97 percent, 98 percent, 99 percent or 100 percent. In addition, any numerical ranges defined by two R numbers as defined above are also specifically described. The use of the term "optionally" with respect to either element of a claim means that the element is required or, alternatively, the element is not required, both alternatives being within the scope of the claim. The use of broader terms, such as comprises, includes, and having, should be understood to provide support for more narrow terms, such as consisting of, consisting essentially of, and comprising substantially of.
[00341] Consequently, the scope of protection is not limited by the description given above but is only limited by the claims that follow, the scope of which includes all equivalents of the subject matter of the claims. Each and all claims are incorporated into the specification as an embodiment of the present description. In this way, the claims are a further description and are in addition to the embodiments of the present description. The discussion of a reference herein is not an admission that this is prior art of the present invention, especially any reference that may have a publication date after the priority date of this application. Descriptions of all patents, patent applications, and publications cited herein are incorporated herein by reference, to the extent that they provide examples, procedures, or other details in addition to those presented herein.

权利要求:
Claims (30)
[0001]
1. A reactive distillation method, characterized in that it comprises: introducing a feed stream to a reactive distillation column, wherein the feed stream comprises one or more alpha hydrogen alcohols; contacting the feed stream with one or more catalysts in the reactive distillation column during a distillation, wherein the feed stream reacts in contact with one or more catalysts to produce a reaction product comprising one or more higher alcohols, wherein the one or more higher alcohols refers to alcohols having a higher molecular weight than the corresponding one or more alpha hydrogen alcohols in the feed stream, and wherein the one or more higher alcohols comprises a C4-C13 alcohol, and removing the one or more higher alcohols during the distillation of the reactive distillation column as a lower stream.
[0002]
2. Method according to claim 1, characterized in that the one or more alpha hydrogen alcohols comprise one or more of ethanol, propanol or butanol.
[0003]
3. Method according to claim 1, characterized in that the one or more alpha hydrogen alcohols comprise only ethanol.
[0004]
4. Method according to any one of the preceding claims, characterized in that the one or more higher alcohols comprise a C4-C13 alcohol, preferably wherein the one or more higher alcohols comprise at least one alcohol selected from the group consisting of : 1-butanol, 1-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-ethyl-2-hexanol, heptanol, decanol and dodecanols.
[0005]
5. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise a magnesium oxide catalyst.
[0006]
6. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise a hydroxyapatite Guebert reaction catalyst.
[0007]
7. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise CuO/SiO2, CuO/SiO2-Al2O3, CuO/ZnO, CuO/ZrO2, CuO/SiO2-ZrO2 CuO /Al2O3, CuO/MgO, CuO/MgO/SiO2, CuO/MgO/Al2O3, CuO/ZnO/SiO2, CuO/ZrO2/SiO2, CuO/MgO/SiO2, CuO/CaO/SiO2, CuO/SrO/SiO2, CuO /BaO/SiO2, CuO/ZrO2/Al2O3/SiO2, CuO/Na2O/SiO2, CuO/MgO/Al2O3/SiO2 CuO/CeO2/MgO/Al2O3, CuO/ZnO/Al2O3, CuO/Cr2O3/Al2O3 and CuO/ZrO2/ Al2O3, or any combination thereof, and wherein the catalyst has a copper weight loading of between 0.5% and 80% of the catalyst.
[0008]
8. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise a catalyst component represented by the formula: M/MgO/Al2O3, where M represents palladium, rhodium, platinum, silver, gold, nickel, or copper, or oxides thereof, alternatively wherein the one or more catalysts comprise a hydroxyapatite represented by the formula: Ca10(PO4)6(OH)2 wherein the ratio of calcium to phosphorus (Ca:P) is between 1.5 and 1.8.
[0009]
9. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise at least one catalyst component selected from the group consisting of: copper, copper oxide, barium, barium oxide, zinc, zinc oxide, zirconium, zirconium oxide, magnesium, magnesium oxide, aluminum, aluminum oxide, chromium, chromium oxide, iron, iron oxide, sodium, sodium oxide, sodium carbonate, strontium, oxide strontium, tin, tin oxide and any mixture thereof.
[0010]
10. Reactive distillation method according to any one of the preceding claims, characterized in that the one or more catalysts comprise a support, wherein the support comprises at least one support material selected from the group consisting of: carbon, silica , silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride, boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, a zeolite, a carbon nanotube, carbon fullerene, and any combination thereof.
[0011]
11. Reactive distillation method according to any one of the preceding claims, characterized in that it further comprises: removing a side stream from the reactive distillation column; contacting the side stream with a secondary reactor catalyst, wherein the side stream reacts in the presence of the secondary reactor catalyst to produce at least one of the one or more higher alcohols and reintroduce the at least one of the one or more higher alcohols produced in the presence of the secondary reactor catalyst in the reactive distillation column.
[0012]
12. Reactive distillation method according to claim 11, characterized in that the secondary stream comprises a steam and wherein contacting the secondary stream with the secondary reactor catalyst comprises contacting the steam with the secondary reactor catalyst, or alternatively wherein the side stream comprises a liquid and wherein contacting the side stream with the secondary reactor catalyst comprises contacting the liquid with the secondary reactor catalyst.
[0013]
13. Reactive distillation method according to claim 11, characterized in that it further comprises: adjusting a sidestream flow rate to increase the production of the one or more higher alcohols.
[0014]
14. Reactive distillation method according to claim 1, characterized in that it further comprises: removing a plurality of side streams from the reactive distillation column; feeding each of the plurality of side streams into a corresponding plurality of a corresponding plurality of side reactors, wherein each of the plurality of side reactors comprises at least one secondary reactor catalyst; contacting each of the plurality of side streams with the at least one secondary reactor catalyst in the corresponding plurality of side streams, wherein each of the plurality of side streams reacts in the presence of the one or more secondary reactor catalyst to produce a higher alcohol and reintroducing the upper alcohol produced in the presence of the secondary reactor catalyst from each of the plurality of side reactors in the reactive distillation column.
[0015]
15. Reactive distillation method according to any one of the preceding claims, characterized in that it further comprises: adjusting a reactive distillation column pressure to increase the production of the one or more higher alcohols.
[0016]
16. Reactive distillation method according to any one of the preceding claims, characterized in that it further comprises introducing a second feed stream comprising hydrogen into the reactive distillation column.
[0017]
17. Reactive distillation method according to any one of the preceding claims, characterized in that it further comprises: removing the lower stream from the reactive distillation column, wherein the one or more higher alcohols comprise one or more C6-C13 and butanol; separating at least a portion of the one or more C6-C13 alcohols from the one or more C2-C5 alcohols and recycling the one or more C2-C5 alcohols into the reactive distillation column.
[0018]
18. Reactive distillation method according to claim 1, characterized in that the feed stream still comprises water.
[0019]
19. Method according to claim 1, characterized in that it further comprises: separating the lower stream into an upper stream and a second lower stream into a separation unit, wherein the lower stream comprises water, butanol and one or more esters, wherein the upper stream comprises water and the one or more esters, and wherein the lower stream comprises butanol; passing a stream above a decanter; generating, in the decanter, a phase comprising substantially all of the water and an organic phase comprising the one or more esters; removing the aqueous phase from the decanter as an aqueous stream; removing the organic phase from the decanter as an organic stream; separating the organic stream into a product stream and a recycle stream, wherein the product stream comprises the one or more esters and wherein the recycle stream comprises water.
[0020]
20. Method according to claim 19, characterized in that the one or more esters comprise one or more of ethyl butyrate, ethyl acetate, or butyl acetate.
[0021]
21. Method according to claim 1, characterized in that the method further comprises: separating the lower stream into an upper stream and a second lower stream into a separation unit, wherein the lower stream comprises water, either one or more higher alcohols and one or more esters, wherein the upper stream comprises water, the one or more esters and a first portion of the one or more higher alcohols and wherein the second lower stream comprises a second portion of the one or more higher alcohols ; separating the second lower stream into at least one product stream comprising a first higher alcohol from the first portion of the one or more higher alcohols; passing a stream above a decanter; generating, in the decanter, a phase comprising substantially all of the water and an organic phase comprising the one or more esters and the second portion of the one or more higher alcohols; removing the aqueous phase from the decanter as an aqueous stream; removing the organic phase from the decanter as an organic stream and separating the organic stream into a first stream comprising the one or more esters and a second stream comprising the second portion of the one or more higher alcohols.
[0022]
22. The method of claim 21, characterized in that separating the second lower stream into at least one product stream comprises: separating the second lower stream into a first product stream comprising butanol and a second product stream comprising comprises a remainder of the first portion of the one or more higher alcohols.
[0023]
23. The method of claim 21, wherein separating a second lower stream into at least one product stream further comprises: separating the remainder of the first portion of the one or more higher alcohols into a third product stream comprising hexanol.
[0024]
24. Method according to claim 21, characterized in that separating the organic stream into a first stream comprising the one or more esters and a second stream comprising the second portion of the one or more higher alcohols comprises: separating the stream organic in a second upper stream comprising the one or more esters and water and a third lower stream comprising the second portion of the one or more higher alcohols.
[0025]
25. Method according to claim 24, characterized in that separating the organic stream into a first stream comprising the one or more esters and a second stream comprising the second portion of the one or more higher alcohols further comprises: passing the second stream greater than a second decanter; generating, in the second decanter, a second aqueous phase comprising substantially all of the water in the organic stream and a second organic phase comprising the esters; removing the second aqueous phase from the second decanter as a second aqueous stream; removing the second organic phase from the second decanter as a second stream of organics; separating the second stream of organics into a product stream of esters comprising the one or more esters.
[0026]
26. Method according to claim 24, characterized in that separating the organic stream into a first stream comprising the one or more esters and a second stream comprising the second portion of the one or more higher alcohols further comprises: separating the third lower stream into a third upper stream and a fourth lower stream, wherein the third upper stream comprises at least one higher alcohol of the second portion of the plurality of higher alcohols.
[0027]
27. Method according to claim 24, characterized in that separating the third lower stream into the third upper stream and the fourth lower stream occurs at a pressure greater than 3 atmospheres.
[0028]
28. Method according to claim 21, characterized in that separating the organic stream into the first stream comprising the one or more esters and the second stream comprising the second portion of the one or more higher alcohols takes place in a distillation system , wherein the distillation system comprises a distillation column and at least one rectifier or extractor in fluid communication with a distillation column.
[0029]
29. Reactive distillation system, characterized in that it comprises: a reactive distillation column comprising: a catalyst located generally centrally in the column, an ethanol feed in fluid communication with the reactive distillation column and configured for passing ethanol over the catalyst, wherein the catalyst is configured to convert at least a portion of the ethanol feed to butanol in the reactive distillation column; an upper product dewatering passage and an upper lower product alcohol removal passage; a product separation system comprising an inlet configured to receive bottom product from the reactive distillation column, an upper alcohol product removal passage and an ethanol removal passage, and a recycle line connecting the removal passage. ethanol from the product separation system and an inlet to the reactive distillation column.
[0030]
30. Reactive distillation system according to claim 29, characterized in that the reactive distillation column comprises a continuous stirred tank reactor (CSTR) configured to contact a liquid ethanol feed with the catalyst and remove water during contact of the liquid ethanol feed with the catalyst.

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同族专利:

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公开号 | 公开日

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CA2899318C|2019-12-24|

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CN105073697B|2017-05-24|

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US20140235901A1|2014-08-21|

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WO2014130465A1|2014-08-28|

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BR112015019704A8|2021-02-09|

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CN105073697A|2015-11-18|

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BR112015019704A2|2017-07-18|

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CA2899318A1|2014-08-28|

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MY170550A|2019-08-16|

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法律状态:
2018-04-24| B25A| Requested transfer of rights approved|Owner name: RESCURVE, LLC (US) |

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2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-04-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-07-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361766484P| true| 2013-02-19|2013-02-19|

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US61/766,484|2013-02-19|

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US201361912235P| true| 2013-12-05|2013-12-05|

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US61/912,235|2013-12-05|

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PCT/US2014/016957|WO2014130465A1|2013-02-19|2014-02-18|Production of higher alcohols|

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