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    • 专利摘要:
    Ethylene glycol is prepared from a carbohydrate source by reacting the carbohydrate source with hydrogen in a continuous process, in which hydrogen, the carbohydrate source and a liquid diluent are continuously fed into a continuous stirred reactor in which a catalyst system a catalyst system is present which comprises a tungsten compound and at least one hydrogenolysis metal selected from groups 8, 9 or 10 of the Periodic Table of Elements, to obtain the reaction between the carbohydrate and hydrogen source to ethylene glycol; wherein continuously a mixture of product comprising ethylene glycol and diluent is removed from the continuous stirred reactor; and wherein continuously or periodically thereafter at least one tungsten compound is added to the continuous stirred reactor (CSTR).
    公开号:BR112017014945B1
    申请号:R112017014945-1
    申请日:2016-01-13
    公开日:2021-06-08
    发明作者:Jan Cornelis Van Der Waal；Gerardus Johannes Maria Gruter
    申请人:Avantium Knowledge Centre B.V.；
    IPC主号:
    专利说明:

    [001] The present invention relates to a continuous process for the preparation of ethylene glycol from a carbohydrate source. Specifically, it relates to a process for preparing ethylene glycol from a sustainable carbohydrate resource using a specific catalyst system.
    [002] The catalytic conversion of carbohydrates from a sustainable resource into valuable chemicals such as alkylene glycols has gained interest. Alkylene glycols are interesting chemicals which find application in the preparation of polyesters, such as poly(alkylene terephthalate), poly(alkylene naphthenate) or poly(alkylene furandicarboxylate). Other applications of alkylene glycols, in particular ethylene glycol, include their use as an antifreeze. By enabling the preparation of such chemicals from sustainable resources, dependence on fossil fuel resources is reduced. As there is a desire to reduce dependence on fossil fuels, there is an increasing need for sustainable resources for the production of alkylene glycols such as ethylene glycol.
    [003] In US 7,960,594, a process is described in which ethylene glycol is produced from cellulose. This process involves catalytic degradation and hydrogenation reactions under hydrothermal conditions. More specifically, the process is carried out by contacting cellulose at high temperature and pressure with a catalyst system comprising two types of components active in the presence of hydrogen. The first active component comprises tungsten or molybdenum in its metallic state or its carbide, nitride or phosphide. The second component is selected from the hydrogenation metals of Groups 8, 9 and 10 of the Periodic Elements Table, and includes cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum. In experiments, catalyst compounds were used in a carrier, like activated carbon. Furthermore, it appears that the reaction conditions that result in satisfactory yields include a temperature of 220 to 250°C and a hydrogen pressure of 3 to 7 MPa (measured at room temperature). When a 1% by weight cellulose slurry is subjected to these compounds for 30 minutes, ethylene glycol is obtained in yields of up to 69%. However, it also appears that when the reaction is continued for an extended period, the yield of ethylene glycol reduces.
    [004] This reaction was further studied in catalyst systems containing nickel and tungsten in a carrier. There, nickel and tungsten were found to leach into the solution during the reaction, which explains the gradual deterioration of catalyst performance (cf. Na Ji et al., ChemSusChem, 2012, 5, 939-944). Leaching of tungsten and other metals was confirmed in the study reported in M. Hing et al., Chin. J. Catal., 35 (2014) 602-613. The last document also describes that, in addition to ethylene glycol, different by-products are obtained, including 1,2-propylene glycol, erythritol, glycerol, mannitol and sorbitol.
    [005] US 2011/0312488 describes a catalyst system for the generation of alkylene glycols from a carbohydrate as a potential alternative to a catalyst comprising metal components in the elemental state; such catalyst system comprises at least one metal with an oxidation state of at least +2. More specifically, that US application describes a catalyst system comprising a first metal component having an oxidation state of at least +2 and a hydrogenation component. The hydrogenation component can be selected from a wide range of metals in any oxidation state, including the elemental state. The hydrogenation component may in particular comprise an active metal component selected from the group consisting of Pt, Pd, Ru,Rh, Ni, Ir and combinations thereof. The first metal component can also be selected from a range of metals, but in particular the compounds comprising the first metal component can be selected from the group comprising tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group 1 or 2 element, metatungstate compounds comprising at least one Group 1 or 2 element, paratungstate compounds comprising at least one Group 1 or 2 element, tungsten oxides, tungsten heteropoly compounds and various salts and oxides of molybdenum, niobium, vanadium, zirconium, titanium and chromium. The catalyst system according to US 2011/0312488 is indicated to improve the selectivity for ethylene glycol and propylene glycol, with a reduced production of butane diols. The generation of ethylene glycol is shown in some experiments, indicating that ammonium metatungstate is the preferred first metal component and that, as the preferred hydrogenation component, platinum or nickel can be used. The use of nickel-containing catalyst systems results in higher yields of ethylene glycol and optionally propylene glycol.
    [006] In the article mentioned above by M. Zheng et al., Chin. J. Catal., 35 (2014) 602-613, it is concluded that tungsten acid-based catalysts are the most promising candidates for the future commercialization of the cellulose to ethylene glycol process. A hydrogenation component is added to such tungsten acid based catalysts. Examples include ruthenium in activated carbon, but Raney nickel is considered the most promising candidate for commercialization.
    [007] The conversion of a carbohydrate into alkylene glycol involves complex reactions. It was shown in M. Zheng et al., Chin. J. Catal., 35 (2014) 602-613, that lower concentrations of carbohydrates and high reaction temperatures, ie, above 200 C, are beneficial for the production of ethylene glycol. This appears to be confirmed in WO 2014/161852 describing experiments in which glucose solutions with increasing glucose concentrations in the range of 1% by weight to 6% by weight were brought into contact with hydrogen in the presence of a catalyst system comprising tungsten and ruthenium. The higher the concentration of glucose, the lower the yield of ethylene glycol. To remedy this disadvantageous effect, it is proposed in WO 2014/161852 to contact a first small portion of the carbohydrate with hydrogen and the catalyst in a solution with a carbohydrate concentration less than 2% by weight and only when the first portion reacts, add others carbohydrate portions. In this respect, the process is similar to the semi-continuous reactions described in G. Zhao et al., Ind. Eng. Chem. Res., 2013, 52, 9566-9572. Both WO 2014/161852 and G. Zhao et al. in Ind. Eng. Chem. Res., 2013, 52, 95669572 mention that, in addition to ethylene glycol, 1,2-butane diol (butylene glycol) is produced. The relative amount of butylene glycol can be on the order of 10%, based on the yield of ethylene glycol. Since butylene glycol and ethylene glycol form an azeotrope, it is difficult to separate the compounds easily by distillation.
    [008] The above prior art methods were conducted in a batch or semi-batch manner. It would be advantageous to conduct this reaction in a continuous mode. In US 8,410,319 a continuous process is described in which a feedstock containing cellulose is contacted with water, hydrogen and a catalyst to generate at least one alkylene glycol. The catalyst comprises a first metal component selected from the group consisting of Mo, W, V, Ni, Co, Fe, Ta, Nb, Ti, Cr, Zr and combinations thereof. The first metal component is in the elemental state or the metal is the compound of carbide, nitride or phosphide. The catalyst further comprises Pt, Pd, Ru and combinations thereof, wherein the metal is in the elemental state. The catalyst components are comprised in a carrier. The reactor can be a slurry reactor, a drill reactor system, an immobilized catalyst reaction system with catalyst channels, or a boiling bed reactor. These reactors are suitable for a three-phase solid/liquid/gas contact. In a slurry reactor, the catalyst is suspended in the liquid and gas is bubbled through the liquid. Therefore, a slurry reactor is suitable for heterogeneous catalysts. However, the slurry reactor can additionally have the drawback that the reactor can switch on, and that a high liquid to catalyst ratio is required. A boiling bed reactor, also known as a slurry bed reactor, works similarly, but the catalyst bed is substantially retained in the reactor vessel.
    [009] CN102643165 describes a continuous process for the production of ethylene glycol and propylene glycol from soluble sugars or starch and hydrogen. The catalyst system used contains ruthenium and ammonium metatungstate. In one modality, the weight ratio of ruthenium to tungsten is 1:1 and the weight ratio of glucose to the sum of ruthenium and tungsten is 150:1. In other embodiments, the ratio of tungsten to ruthenium is 5 or 10, and the ratio of glucose weight to the sum of ruthenium and tungsten is 750 to 800 or 450 to 460, respectively. After the reaction, the effluent is separated. Dissolved tungsten components are recovered and recycled for the reaction. The reaction is conducted in a hydrogenation reactor which is filled with a slurry of a ruthenium on active carbon catalyst and tungsten catalyst. Hydrogen enters from the bottom and stirs the catalyst slurry. The reactor is therefore a slurry reactor.
    [0010] It has been found that the reactors described above are less suitable for reactions in which one or more catalyst components dissolve or leach into the liquid. It has now been found that a continuous stirred tank reactor solves this problem.
    [0011] Consequently, the present invention provides a continuous process for the preparation of ethylene glycol from a carbohydrate source by reacting the carbohydrate source with hydrogen, wherein the hydrogen, the carbohydrate source and a liquid diluent are fed continuously in a continuous stirred tank reactor in which there is a catalyst system, which catalyst system comprises a tungsten compound and at least one hydrogenolysis metal selected from groups 8, 9 or 10 of the Periodic Table of Elements, to obtain the reaction between the carbohydrate and hydrogen source for ethylene glycol; wherein continuously a product mixture comprising ethylene glycol and diluent is removed from the continuous stirred tank reactor; and wherein, continuously or periodically, at least one tungsten compound is added to the continuous stirred tank reactor.
    [0012] The continuous stirred tank reactor (CSTR) is perfectly suited for this reaction, since through the addition of tungsten, the loss of tungsten, which can be through the addition of a homogeneous or heterogeneous tungsten compound, which it is leached from the catalyst system in the CSTR, is overcome and through continuous addition of the reactants and continuous removal of the product mixture while mechanically agitating the reactants, an equilibrium state situation can easily be created. This allows for consistent high conversion and high reaction selectivity. In this way, the amount of tungsten is supplemented. Since the hydrogenolysis metal hardly leachs out, there may be no need to add additional hydrogenolysis metal to the CSTR as well. If and to the extent that any hydrogenolysis catalyst is removed from the CSTR during the reaction, this can be supplemented by periodic or continuous addition of it to the CSTR. Additional advantages of using a CSTR in the present process will become evident later.
    [0013] The carbohydrate source can be selected from a variety of sources. Suitably, the carbohydrate source comprises or consists of a carbohydrate selected from the group consisting of polysaccharides, oligosaccharides, disaccharides and monosaccharides. Suitable examples include sustainable sources such as cellulose, hemicellulose, starch, sugars such as sucrose, mannose, arabinose, glucose and mixtures thereof. Sources containing the above carbohydrates can include pulp streams, municipal wastewater streams and other streams containing glucose units can also be used, for example, from wood waste, paper waste, agricultural waste, municipal waste, paper, cardboard, sugar cane, sugar beet, wheat, rye, barley, other agricultural crops and combinations thereof. These streams may require pre-treatment to remove components that interfere with the current process, such as base fillers, eg calcium carbonate in waste paper. In this way, the process according to the invention can not only be used from natural sources, but can also be used to update and reuse waste streams in a useful way. Preferably, the carbohydrate in the carbohydrate source is selected from the group consisting of cellulose, starch, glucose, sucrose, glucose oligomers, waste paper and combinations thereof, most preferably glucose or starch. Since cellulose presents difficulties that are absent in other carbohydrate sources, the carbohydrate source is most preferably selected from the group consisting of starch, hemicelluloses and hemicellulose sugars, glucose and combinations thereof.
    [0014] As shown in the known processes according to the prior art, the hydrogenolysis metal can be selected from a wide range of metals. The hydrogenolysis metals may suitably be selected from the group consisting of Cu, Fe, Ni, Co, Pt, Pd, Ru, Rh, Ir, Os and combinations thereof. Preferably, the hydrogenolysis metal is selected from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof. These metals have been found to produce good yields. The metal may suitably be present in its metallic form or as a hydride or oxide. It is assumed that the metal oxide is reduced during the reaction in the presence of hydrogen.
    [0015] The hydrogenolysis metal or combination of hydrogenolysis metals is preferably present in the form of a catalyst supported on a carrier. The carrier can be selected from a wide range of known supports. Suitable supports include activated carbon, silica, zirconia, alumina, silica-alumina, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolitic aluminum silicates, titanosilicates, magnesia, silicon carbide, clays and blends of the same. The knowledgeable person will know that activated carbon is an amorphous form of carbon with a surface area of at least 800 m2/g. Such activated carbon therefore has a porous structure. The most preferred supports are activated carbon, silica, silica-alumina and alumina, as they obtained excellent results with them. More preferably, the catalyst comprises ruthenium as the hydrogenolysis metal and activated carbon as the support.
    [0016] Suitably, more than one metal is used in the catalyst component comprising the hydrogenolysis metal. Suitably, the hydrogenolysis metal combination comprises at least one noble metal selected from Pd, Pt, Ru, Rh and Ir in combination with another metal from groups 8, 9 or 10 of the Periodic Table of Elements. The catalyst preferably comprises a mixture of two or more metals from the group consisting of Ru, Pt, Pd, Ir and Rh. Suitable examples are Ru/Ir, Ru/Pt, Ru/Pd. When two metals are used, the weight ratio is suitably in the range of 0.1:1 to 20:1. More preferably, a first hydrogenolysis metal is ruthenium and a second hydrogenolysis metal is selected from Rh, Pt, Pd and Ir. The weight ratio between Ru and second hydrogenolysis metal is preferably in the range of 0.5:1 to 10:1.
    [0017] The catalyst system also comprises a tungsten compound. This tungsten compound can be selected from a wide range of compounds. Tungsten can be in the elemental state. Typically, the tungsten compound is present in a support. Similar to supports for at least hydrogenolysis metal, the support can be selected from a wide range of known supports. Suitable supports include active carbon, silica, zirconia, alumina, silica-alumina, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolitic aluminosilicates, titanosilicates and combinations thereof. The most preferred ones are activated carbon, silica, silica-alumina and alumina as support, since they obtained excellent results with them. It is also possible to use tungsten compounds in an oxidation state of up to +2, as in the form of their carbide, nitride or phosphide. Also in this case, the tungsten compound may be present in the form of a supported catalyst component. The carrier can be selected from the brackets described above.
    [0018] Preferably, the tungsten compound has an oxidation state of at least +2, preferably having an oxidation state of +5 or +6. The tungsten compound is then suitably selected from the group consisting of tungstic acid (H2WO4), ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one element from Group 1 or 2, metatungstate compounds comprising at least minus one Group 1 or 2 element, paratungstate compounds comprising at least one Group 1 or 2 element, tungsten oxide (WO3), tungsten heteropolycompounds and combinations thereof. Whereas, in the prior art, it has been found that certain tungsten compounds have leached from their supports and this has been considered a disadvantage, the present inventors have found it advantageous to use tungsten compounds which dissolve in the reaction mixture. It was found that the catalytic activity of the tungsten compound increases if the tungsten compound is dissolved. Without wishing to be bound by any theory, it is believed that, in the reducing atmosphere that is created in the reaction zone through the presence of hydrogen and carbohydrates, hexavalent tungsten compounds can be reduced to pentavalent tungsten and dissolve in the diluent. In this partially reduced state, tungsten ions are effective in attacking carbon-carbon bonds in the carbohydrate source to form alkylene glycol precursors. Therefore, it is believed that tungsten compounds are present in CSTRs in various oxidation states. Such tungsten compounds may include the preferred compounds mentioned above. Other tungsten compounds may also be viable. The tungsten compound that is continuously or periodically added to the CSTR is therefore suitably a compound that has an oxidation state of at least +2. More preferably, the tungsten compound that is continuously or periodically added to the CSTR is selected from the group consisting of tungstic acid (H2WO4), ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one element of the Group 1 or 2, metatungstate compounds comprising at least one element from Group 1 or 2, paratungstate compounds comprising at least one element from Group 1 or 2, tungsten oxide (WO3), tungsten heteropolycompounds and combinations thereof. A preferred tungsten compound is tungstic acid.
    [0019] The amount of tungsten that is added to the CSTR is preferably such that the concentration of tungsten in the CSTR is substantially constant. In this descriptive report, it is understood by substantially constant that the difference between the highest and lowest amounts of tungsten does not vary by more than 10% of the average amount of tungsten in the CSTR. Since it is feasible to add tungsten periodically, it is more convenient to provide a continuous addition of tungsten to the CSTR. The added amount is then suitably adjusted so that it is equal to the amount of tungsten that is leached from the catalyst system into the CSTR and is removed therefrom with product mixing. In this way, a consistent performance of the CSTR is possible.
    [0020] According to the prior art, the ratio between the at least one hydrogenolysis metal and the tungsten compound can vary over wide ranges. According to the prior art, the weight ratio between these components can range from 0.02 to 3000. In the present invention, the molar ratio of tungsten to the at least one hydrogenolysis metal is preferably in the rather narrow range of 1 to 25 Preferably, the molar ratio of tungsten to the at least one hydrogenolysis metal is in the range from 2 to 20, more preferably from 5 to 15. If the ratio is beyond the limits of these ranges, the relative yield of alkylene glycols other than ethylene glycol decreases and/or carbohydrate conversion is decreased. Expressed by weight, the weight ratio of tungsten to the at least one hydrogenolysis metal, all calculated as metals, in the CSTR is preferably in the range from 2 to 50 w/w, more preferably from 5 to 50 w/w.
    [0021] The concentration of catalyst components may vary in the process according to the present invention. The concentration of the tungsten compound can vary over very wide ranges. The concentration of the tungsten compound according to prior art batch processes can, for example, be selected from the range of 1 to 35% by weight, based on the weight of the carbohydrate source introduced into the reaction zone. The amount of metal or metals from hydrogenolysis can also vary. It is preferable to apply a concentration greater than that described in CN102643165. According to the embodiments of this prior art document, the maximum concentration of hydrogenolysis metal, i.e. ruthenium, is 1:300, based on the amount of ruthenium and the amount of carbohydrate introduced into the reactor. In the CSTR reactor which is applied in the process of the present invention, the weight ratio of hydrogenolysis metal and carbohydrate which is introduced into the CSTR is preferably in the range from 1:25 to 1:250 w/w, preferably from 1:50 to 1 :200 p/w. Without wishing to be bound by any theory, it is believed that at such a high concentration of hydrogenolysis metal, the formation of humins is prevented and the conversion of carbohydrates to glycols is enhanced. Furthermore, the conversion can then be kept in a steady state. In a high converting CSTR under steady state conditions, the amount of carbohydrate remaining in the reaction mixture is very low. Depending on the carbohydrate conversion that is adjusted, the weight ratio of the tungsten compound, calculated as metal, in the CSTR to the carbohydrate in the CSTR is advantageously in the ranges of 5 to 50 w/w. The amount of carbohydrate source in the CSTR is very different from the concentration of the amount of carbohydrate being introduced into the CSTR unit over time. The remaining concentration of carbohydrates in the CSTR is much lower. This represents a big difference between the prior art batch and semi-batch processes and the present continuous process. By adjusting the reaction conditions, including residence time, the person skilled in the art can arrange for a fixed carbohydrate source conversion. This conversion will result in a small amount of unconverted carbs remaining in the CSTR. Under steady-state conditions, this small amount will be kept constant.
    [0022] The carbohydrate source and the diluent are both introduced into the CSTR. Suitably, the carbohydrate source is introduced together with at least part of the diluent. More preferably, the carbohydrate source is at least partially dissolved in the diluent. Suitably the diluent is an aqueous medium. Many carbohydrates like sugars, glucose and fructose are water soluble. Furthermore, cellulose, i.e. a carbohydrate which is considered to be a very suitable starting material, and which is insoluble in water, can be converted to cellodextrins which are soluble in water. Alternatively, the carbohydrate can be introduced into the reaction zone as a slurry. The most common examples of such slurries are aqueous mixtures of water and cellulose and/or starch. In such embodiments, aqueous cellulose slurries, containing, for example, microcrystalline cellulose can suitably be used.
    [0023] The present process allows the use of a very concentrated feed stream containing the carbohydrate source. By employing a concentrated feed stream, process economics is benefited. However, it is not necessary to use a concentrated supply current. Such a feed stream will generally comprise the carbohydrate source and at least part of the diluent. The feed stream comprising the carbohydrate source and the diluent suitably has a concentration of 1 to 50% by weight, based on the weight of the carbohydrate source and the diluent. When a supply current is used within this concentration range, the supply current is generally easily transportable. Concentration is not limited to values within this range. The supply current, for example, can also consist only of the carbohydrate source. Typically, such a supply stream is then solid. By introducing the solid carbohydrate into the CSTR at the desired feed rate, the carbohydrate source is dissolved in the reaction mixture and converted.
    Prior art processes focus on the conversion of hexoses such as cellulose, starch and glucose. However, it has been found to be advantageous to use not only carbohydrates containing hexose, but also carbohydrates containing pentose. Therefore, the present invention also provides a process wherein the carbohydrate source comprises at least one pentose containing carbohydrate or, preferably, the carbohydrate source comprises a combination of at least one pentose containing carbohydrate and at least one hexose containing carbohydrate. The pentose-containing carbohydrate can be a polysaccharide, an oligosaccharide, a disaccharide or a monosaccharide. The pentose-containing carbohydrate is suitably a pentosan, for example xylan or arabinan. In particular, it suitably comprises at least one of the radicals arabinose, ribose, garbagese and xylose. The application of the process according to the present invention in a combination of hexose and pentose containing carbohydrates has the advantage that the pentose containing carbohydrate yields both propylene glycol and ethylene glycol as main products and the hexose containing carbohydrates yield a majority of ethylene glycol. Thus, when propylene glycol is considered as the main by-product, it is beneficial to use carbohydrates containing pentose as the starting material. It is evident that the carbohydrate source comprising hexose and pentose units can be obtained by mixing a separate hexose and a separate pentose fraction. Alternatively, the carbohydrate source can be the product of a natural source that already contains pentose and hexose units. It can, for example, be the product of hydrolysis of lignocellulosic biomass, which hydrolysis results in pentoses and hexoses.
    [0025] A high concentration of carbohydrates in the diluent can pose problems regarding the solubility of the carbohydrate source. To avoid major problems, water is typically used as a thinner, as carbohydrates tend to be less soluble in most organic thinners. However, water can optionally be partially substituted or mixed with organic diluents which have a beneficial effect on the solubility of any of the reactants or have any other advantage. Accordingly, the diluent comprises one or more of the compounds selected from the group consisting of water, sulfoxides, alcohols, amides and mixtures thereof. Suitably a mixture of water and optionally one or more of the above mentioned organic diluents is used. A suitable sulfoxide is dimethyl sulfoxide (DMSO); suitable examples of amides are dimethyl formamide and dimethyl acetamide. The most preferred organic diluents are alcohols. The alcohols can be monoalcohols, in particular water miscible monoalcohols such as C1-C4 alcohols. The alcohol can also be a polyol, for example glycerol, xylitol, sorbitol or erythritol. In a particularly preferred embodiment, the polyol is a diol. It is more preferred that the organic diluent is an alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol or a mixture thereof.
    [0026] The use of alkylene glycol is particularly suitable, as it has been found that polyols, including alkylene glycols, facilitate the dissolution of the tungsten compound in the diluent, thus promoting the catalytic activity of the tungsten compound. It has further been found that the selectivity of the reaction to alkylene glycols is enhanced by the use of alkylene glycol as a component in the diluent. Without wishing to be bound by any theory, it is believed that tungsten forms complexes with alkylene glycol, whereby conversion to by-products is reduced. Furthermore, the use of an alkylene glycol as a diluent does not involve introducing a foreign reagent into the reaction mixture, which is an additional advantage. Since alkylene glycols tend to facilitate the solubility of the tungsten compound, it is advantageous to periodically or continuously introduce tungsten into the CSTR along with an alkylene glycol. This has the advantage that the dosage of the desired amount of tungsten can easily be carried out. Furthermore, since the reaction produces alkylene glycols, in particular ethylene glycol, the addition of alkylene glycol does not introduce a foreign compound into the CSTR. Preferably, tungsten is introduced into the CSTR together with ethylene glycol. Such an alkylene glycol for use as a diluent component can be obtained from the reaction. Therefore, a portion of the alkylene glycols that are produced in the process of the present invention can be recycled to the CSTR as diluents for the carbohydrate and/or tungsten catalyst component.
    [0027] As indicated above, the ethylene glycol containing product of the process according to the present invention is generally a mixture of alkylene glycols. This mixture is suitably purified, especially when pure ethylene glycol is desired for polymerization purposes. The azeotrope that is formed with butylene glycol makes it difficult to obtain pure ethylene glycol.
    [0028] To facilitate the separation process, it is advantageous to use carbohydrate containing pentose as the starting material, alone or in addition to the carbohydrate containing hexose. Carbohydrates containing pentose form almost no butylene glycol as a by-product. Thus, the proportion of butylene glycol in the reaction product of a combination of carbohydrates containing pentose and hexose will be relatively small. Purification of such a reaction product is therefore relatively simple. Propylene glycol and ethylene glycol can be easily separated from each other through fractionation. Fractionation of the reaction product with a starting material comprising carbohydrates containing pentose and hexose will result in pure ethylene glycol, pure propylene glycol and a relatively small fraction containing butylene glycol with one or both of the other glycols.
    [0029] Another method to remove butylene glycol from products would be using one or more carriers. The carrier selectively removes butylene glycol from a mixture of alkylene glycols through azeotropic distillation. Such a procedure can be applied to processes where the starting material comprises only hexose-containing carbohydrates, only pentose-containing carbohydrates, or a combination of both. The scavenger may suitably be selected from the group consisting of scavengers selected from ethyl benzene, p-xylene, n-propyl benzene, o-diethyl benzene, m-diethyl benzene, m-diisopropyl benzene, cyclopentane, methyl cyclohexane , 3-methyl pentane, 2,3-dimethyl butane, heptane, 1-heptene, octane, 1-octene, 2,3,4-trimethyl pentane, decane, methyl ethyl ketoxime, decalin, dicyclopentadiene, alpha-phelandrene, beta -pinene, myrcene, terpinolene, p-mint-1,5-diene, 3-carene, limonene and alpha-terpinene.
    [0030] Furthermore, higher polyols such as glycerol, erythritol or sorbitol can function as a carrier. These compounds tend to be produced as by-products in the process of preparing ethylene glycol from carbohydrates, as shown in M. Zheng et al., Chin. J. Catal., 35 (2014) 602-613. These compounds can therefore be recycled into the process. If necessary, one or more of these compounds can also be added to the product of the present process in order to intensify their concentrations and thus facilitate obtaining pure ethylene glycol when they are used as carriers.
    [0031] In another process for producing pure ethylene glycol, the product mixture comprising ethylene glycol, propylene glycol and butylene glycol can be converted with a compound containing carbonyl group to form a mixture of dioxolanes. These dioxolanes do not form azeotropes and therefore can be separated relatively easily through distillation. After having obtained the pure dioxolanes as separate fractions, each fraction can be hydrolyzed to produce the corresponding pure alkylene glycol. The carbonyl group-containing compound is suitably an aldehyde or ketone. Preferably, it has a boiling point of at least 100°C, so that any water that is introduced into the reaction can be easily separated from the reaction product. Another way to allow an easy separation between water and dioxolanes is to select the carbonyl group-containing compound such that at least some of the resulting dioxolanes are not water-soluble. In this way, the resulting dioxolanes can be separated from water by phase separation. In doing so, any water-soluble by-products are also separated from the dioxolanes. One way to achieve this is by selecting a compound containing a carbonyl group that is insoluble in water itself. Very convenient carbonyl group-containing compounds include methyl isobutyl ketone, t-butyl methyl ketone and mixtures thereof. These compounds have a suitable boiling point in the range of 106 to 118°C and are insoluble in water. Dioxolanes formed with these compounds are also insoluble in water, so separation of these compounds from water is facilitated.
    [0032] The reaction of the compound containing carbonyl group with the alkylene glycols in the product can be catalyzed by means of a catalyst. A suitable catalyst includes an acid catalyst. Although homogeneous acid catalysts can be used, they have the disadvantage that neutralization and/or separation can become cumbersome. Therefore, the acid catalyst is suitably a solid acid catalyst, preferably selected from acidic ion exchange resins, acidic zeolites and combinations thereof. The use of a solid product also facilitates contact between the liquid alkylene glycol mixture and the carbonyl group-containing compound when dioxolane formation is carried out in an extraction column reactor, in which a vapor of the carbonyl group-containing compound is contacted. in countercurrent with a liquid stream of the alkylene glycol mixture when such mixture is passed through the solid acid catalyst. However, it is also feasible to include a homogeneous acid catalyst in the product mixture and pass the carbonyl group-containing compound vapor through this liquid mixture.
    [0033] Once the dioxolanes have been formed, they can be easily separated from each other by distillation. After distillation, the separated dioxolanes can be hydrolyzed to form pure ethylene glycol. The hydrolysis of dioxolanes is conveniently also catalyzed by means of an acid catalyst. Hydrolysis can be achieved similarly to the formation of dioxolanes, for example, by contacting a liquid stream of dioxolane with a countercurrent vaporous stream of water. The acid catalyst can be included in the dioxolane liquid or it can be provided as a solid acid catalyst. The acid catalyst included in the dioxolane liquid can be a strong organic acid, such as p-toluene sulfonic acid or methanesulfonic acid. Preferably, the catalyst is a solid catalyst comprising an acidic ion exchange resin, an acidic zeolite or a combination thereof.
    [0034] As indicated above, the product mixture also comprises tungsten, which is leached from a heterogeneous catalyst system or which results from the addition of a homogeneous tungsten compound. It is desirable to recover tungsten from the product mixture. This can typically be achieved when distillation steps to remove various alkylene glycols from the product mixture were conducted and a distillation residue was obtained. Tungsten can then be recovered by complexation with a polymer, such as polyquaternium-6, and subsequent ultrafiltration, as described in Chin. J.Chem. Eng., 20(2012) 831-836. Alternatively, at least a part of the distillation residue may be acidified, for example with nitric acid, to cause tungstic acid to precipitate. Recovered tungsten compound can be properly recycled to the CSTR. It is also possible to recycle the tungsten through at least part of the distillation residue without separate recovery and isolation of the tungsten compound. In that case, it may be desirable to remove various alcohols and other by-products from the still residue before the remainder is recycled to the CSTR.
    [0035] The process for preparing an alkylene glycol according to the present invention can be carried out under process conditions which are widely known in the art. Conditions include those described in WO 2014/161852. Thus, the reaction temperature is suitably at least 120°C, preferably at least 140°C, more preferably at least 150°C, most preferably at least 160°C. The temperature in the reactor is suitably at most 300°C, preferably at most 280°C, more preferably at most 270°C, even more preferably at most 250°C, and most preferably at most 200°C. The reactor can be brought to a temperature within these ranges prior to the addition of any starting material and is maintained at a temperature within the range.
    [0036] It has been found that the process according to the present invention is most advantageously carried out at temperatures which are generally somewhat lower than those used in prior art processes. It has been found that the formation of butylene glycol is reduced if relatively low temperatures are used. The most advantageous temperature range is from 150 to 225°C, more preferably from 160 to 200°C, and even more preferably from 165 to 190°C. This is contrary to what is taught in US 7,960,594 where a reaction temperature in the range 220 to 250°C was found to be most useful.
    [0037] The process of the present invention takes place in the presence of hydrogen. Hydrogen can be supplied as substantially pure hydrogen. The total pressure will then be the hydrogen pressure. Alternatively, hydrogen can be supplied as a mixture of hydrogen and an inert gas. The total pressure will consist of partial pressures of hydrogen and this inert gas. Inert gas can suitably be selected from nitrogen, argon, helium, neon and mixtures thereof. The ratio of hydrogen to inert gas can vary over wide ranges. Suitably, the ratio is not too low, as the reaction proceeds well when the hydrogen partial pressure is high enough. Therefore, the volume ratio between hydrogen and inert gas can be from 1:1 to 1:0.01. More preferably, only hydrogen is used as a gas in the process according to the invention.
    [0038] Hydrogen is typically supplied through a distributor, eg a spreader, to the CSTR. Through this distributor and through the stirring mechanism, the hydrogen is dissolved in the reaction mixture, thus allowing the reaction of hydrogen with the carbohydrate in the presence of the catalyst system. Hydrogen is held in the CSTR under pressure. Hydrogen pressure is properly maintained at the desired level. Apart from any gas, such as hydrogen, being carried along with the product mixture, no other gas leaves the CSTR.
    [0039] The pressure in the CSTR is suitably at least 1 MPa, preferably at least 2 MPa, more preferably at least 3 MPa. The pressure in the CSTR is suitably at most 16 MPa, more preferably at most 12 MPa, most preferably at most 10 MPa. The knowledgeable person will understand that the pressure at 20°C will be less than the actual pressure at the reaction temperature. The pressure applied in the process is suitably 0.7 to 8 MPa, determined at 20°C. Pressure can be applied by hydrogen gas or a gas containing hydrogen. When a hydrogen-containing gas is used, the hydrogen content in the hydrogen-containing gas is suitably up to 100% by volume, preferably pure hydrogen. The balance of any hydrogen containing gas may suitably be an inert gas such as nitrogen, helium, neon, argon or mixtures thereof. When hydrogen is subsequently heated in the CSTR, the pressure in the reaction is suitably in the range of 1 to 16 MPa. As the reaction proceeds, some hydrogen is consumed. Due to the continuous supply of hydrogen, the partial pressure of hydrogen is conveniently kept substantially constant. Advantageously, the partial pressure of hydrogen at the reaction temperature is kept in the range of 1 to 6 MPa.
    [0040] The reaction time in the process according to the present invention may vary. Suitably, the residence time of the carbohydrate source is at least 1 min. Preferably the residence time is in the range of 5 min to 6 hours, more preferably 5 min to 2 h. In the present continuous process, it is understood that the residence time is the quotient of the mass flow rate of the carbohydrate source in the reaction zone divided by the mass flow rate of the catalyst system in the reaction zone. Generally, the continuous process is operated at a weight hourly space velocity (WHSV), expressed as mass of carbohydrate source per mass of hydrogenolysis metal, expressed as metal, per hour, in the range of 0.01 to 100 hr-1 , preferably from 0.05 to 10 hr-1.
    [0041] When the product mixture is removed from the CSTR, it can be subjected to purification to isolate the desired ethylene glycol and/or other by-products and/or tungsten. When the conversion in the CSTR has been adjusted to a level where the product mixture contains an amount of unconverted carbohydrate source that must be used, it is feasible to feed the product mixture to another reactor where at least the carbohydrate source is in the mixture of the product is brought into contact with another catalyst. Such catalyst can be the same or similar to the catalyst system used in the CSTR. The additional reactor can be selected from any type of reactor, including a plug flow reactor, a slurry reactor, a boiling bed reactor or other CSTR.
    [0042] The invention is illustrated by means of the following example.EXAMPLE 1
    A CSTR equipped with an agitator and having a volume of 3.5 ml was filled with 100 mg of a hydrogenolysis catalyst comprising 5% by weight of ruthenium on active carbon. A feedstock comprising 5% by weight glucose in a mixture of water and glycerol (82% by weight water and 18% by weight glycerol), based on the weight of the mixture, was fed into the CSTR. The feed charge additionally comprised 0.8 g of sodium hydroxide per liter of mixture. The feedstock stream also contained 1 wt% tungstic acid (H2WO4). The reaction temperature was maintained at 200°C, the hydrogen pressure was 50 bar and the stirrer speed was 1000 rpm. The tungsten to ruthenium weight ratio in the experiment was 2.2 w/w. The weight ratio of ruthenium to glucose introduced into the CSTR was 1:115. The liquid feed loading flow was 0.15 ml/min, and the hydrogen flow was 100 ml/min. The residence time of the liquid in the reactor was therefore about 23.3 min. It appeared that the glucose conversion was constant at about 98.5%. The effluent was analyzed and the selectivities in relation to ethylene glycol (sEG), propylene glycol (sPG) and butylene glycol (sBG) were determined. The selectivities were calculated as the amounts of ethylene glycol, propylene glycol and butylene glycol were determined, calculated as the weight percentage in the reactor effluent divided by the amount of glucose being introduced into the CSTR.
    [0044] The results of the experiment at different runtimes are shown in Table 1 below.

    [0045] The results show that the process yields consistent excellent selectivities towards the desired alkylene glycols, in particular for ethylene glycol. EXAMPLE 2
    [0046] To show the effect of catalyst concentration and the effect of glucose concentration, the experiments were carried out in the same manner as in Example 1, with the exception that in one experiment the amount of ruthenium catalyst was 50 mg instead of 100 mg. Thereby, the W/Ru ratio changed to 4.2 w/w and the weight ratio of ruthenium to glucose introduced into the CSTR was 1:230.
    [0047] In another experiment, the glucose concentration was adjusted to 2.5% by weight. The W/Ru ratio was 2.2 p/p and the weight ratio of ruthenium to glucose introduced into the CSTR was 1:115.
    [0048] In addition to the selectivities, glucose conversion is also reported. The results are shown in Table 2.

    [0049] The results show that, with a reduced content of ruthenium, the selectivities in relation to alkylene glycols decrease over time. It appears that humins are formed that accelerate the deactivation of the ruthenium catalyst. Consequently, glucose conversion also decreases over time.
    [0050] With a reduced glucose concentration, the conversion is substantially complete. The selectivity towards ethylene glycol is excellent. The selectivity towards butylene glycol increases over time. When butylene glycol is considered undesirable, it is therefore advantageous to work with higher carbohydrate concentrations.
    权利要求:
    Claims (17)
    [0001]
    1. Continuous process for preparing ethylene glycol from a carbohydrate source by reacting the carbohydrate source with hydrogen, characterized by the fact that hydrogen, the carbohydrate source and a liquid diluent are continuously fed into a continuous stirred reactor in that a catalyst system is present, which catalyst system comprises a tungsten compound and at least one hydrogenolysis metal selected from groups 8, 9 or 10 of the Periodic Table of Elements, to obtain the reaction between the carbohydrate and hydrogen source to ethylene glycol; wherein continuously a product mixture comprising ethylene glycol and diluent is removed from the continuous stirred reactor; and wherein continuously or periodically thereafter at least one tungsten compound is added to the continuous stirred reactor (CSTR), wherein the amount of tungsten that is added to the CSTR is such that its concentration in the CSTR is substantially constant.
    [0002]
    2. Continuous process according to claim 1, characterized in that the weight ratio of tungsten to the at least one hydrogenolysis metal, all calculated as metals, in the CSTR is in the range of 2 to 50 p/w.
    [0003]
    3. Continuous process according to claim 1 or 2, characterized in that the weight ratio of tungsten calculated as metal to carbohydrate source in the CSTR is in the range of 5 to 50 w/w.
    [0004]
    4. Continuous process according to any one of claims 1 to 3, characterized in that the tungsten compound that is continuously or periodically added to the CSTR has an oxidation state of at least +2.
    [0005]
    5. Continuous process according to any one of claims 1 to 4, characterized in that the weight ratio of the at least one hydrogenolysis metal and carbohydrate that is introduced into the CSTR is in the range of 1:25 to 1:250 p /w, preferably from 1:50 to 1:200 w/w.
    [0006]
    6. Continuous process according to any one of claims 1 to 5, characterized in that the tungsten compound which is continuously or periodically added to the CSTR, is selected from the group consisting of tungstic acid (H2WO4), ammonium tungstate , ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group 1 or 2 element, metatungstate compounds comprising at least one Group 1 or 2 element, paratungstate compounds comprising at least one Group element 1 or 2, tungsten oxide (WO3), tungsten heteropoly compounds, and combinations thereof.
    [0007]
    7. Continuous process according to any one of claims 1 to 6, characterized in that the hydrogenolysis metal of groups 8, 9 or 10 of the Periodic Table of Elements is selected from the group consisting of Cu, Fe, Ni, Co, Pd, Pt, Ru, Rh, Ir, Os and combinations thereof.
    [0008]
    8. Continuous process according to any one of claims 1 to 7, characterized in that the at least one hydrogenolysis metal of groups 8, 9 or 10 of the Periodic Table of Elements is present in the form of a catalyst supported on a carrier .
    [0009]
    9. Continuous process according to claim 8, characterized in that the carrier is selected from the group supports, consisting of activated carbon, silica, alumina, silica-alumina, zirconia, titania, niobia, iron oxide, iron oxide tin, zinc oxide, silica-zirconia, zeolitic aluminosilicates, titanosilicates, magnesia, silicon carbide, clays and combinations thereof.
    [0010]
    10. Continuous process according to claim 8 or 9, characterized in that the catalyst system comprises ruthenium in activated carbon.
    [0011]
    11. Continuous process according to any one of claims 1 to 10, characterized in that the carbohydrate source comprises a combination of at least one carbohydrate containing pentose and at least one carbohydrate containing hexose.
    [0012]
    12. Continuous process according to any one of claims 1 to 11, characterized by the fact that the addition rate of the carbohydrate source in the CSTR is such that WHSV is in the range of 0.01 to 100 hr-1.
    [0013]
    13. Continuous process according to any one of claims 1 to 12, characterized in that the diluent is selected from water and optionally one or more organic diluents selected from sulfoxides, alcohols and amides.
    [0014]
    14. Continuous process according to claim 13, characterized in that the organic diluent is an alcohol.
    [0015]
    15. Continuous process according to claim 13 or 14, characterized in that the organic diluent is an alkylene glycol, preferably ethylene glycol.
    [0016]
    16. Continuous process according to any one of claims 1 to 15, characterized in that the temperature in the reaction zone ranges from 120 to 300 °C, preferably from 150 to 225 °C, more preferably from 160 to 200 °C.
    [0017]
    17. Continuous process according to any one of claims 1 to 16, characterized in that the partial pressure of hydrogen in the reaction zone is in the range of 1 to 6 MPa.
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    EP3245181B1|2019-10-23|
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    MX2017009161A|2018-02-01|
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    法律状态:
    2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-04-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/01/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    NL2014121|2015-01-13|
    NL2014121|2015-01-13|
    PCT/NL2016/050029|WO2016114661A1|2015-01-13|2016-01-13|Continuous process for preparing ethylene glycol from a carbohydrate source|
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