Processes for preparing hydrocarbon compositions

专利摘要:
Processes, catalysts and systems for preparing a composition comprising aliphatic, olefinic, cyclic and/or aromatic hydrocarbons of seven or greater carbon atoms per molecule are provided.
公开号:ES2782052A1
申请号:ES202090023
申请日:2018-12-14
公开日:2020-09-09
发明作者:Cross, Jr；Shay Daniel Travis；rui chi Zhang；feng hao Zhang；Fang Zhang
申请人:Invista Textiles UK Ltd；
IPC主号:

专利说明:

[0002] Processes for preparing hydrocarbon compositions
[0004] The patent application claims the priority benefit of the U.S. provisional application no. Serial 62 / 608,111 filed December 20, 2017 and U.S. Provisional Application No. No. 62 / 599,275 filed December 15, 2017, each of which is incorporated herein by reference in its entirety.
[0008] The exploitation of shale gas and shale oil resources in the United States and elsewhere involves the production of substantial quantities of natural gas liquids (NGLs), sometimes called condensates. Such condensates can comprise ethane, propane, butane, pentane, and hexane, for example. While the methane content of shale gas can be used as a source of natural gas, maximizing the value of the "heavier" components is key to maintaining the performance of shale gas production.
[0009] Condensate, in this context, is typically separated from natural gas, ethane, and liquefied petroleum gas (or LPG) in gas separation plants. The condensate comprises straight chain pentane and hexane and both are low octane and have high vapor pressure. As such, it is not suitable for use generally in the gasoline fuel pool. Instead, condensate is used as a feedstock for olefin steam crackers as an alternative to ethane or refinery naphtha, consequently imposing a significantly lower value than gasoline.
[0010] As refineries shift from heavier sources of crude oil to lighter crude oils, originating from shale deposits, the proportion of light paraffinic naphtha generally increases. As a result, the straight run naphtha produced from the crude fractionator contains large amounts of straight chain pentane and hexane, which has a relatively low octane number or unit and a relatively high vapor pressure. Further processing of this stream to reduce the content of Sulfur by hydrotreating further reduces the octane content as a result of hydrogenation of unsaturated species such as olefins.
[0011] One means by which it is possible to increase the octane content is isomerization to increase the proportion of branched paraffins. However, this has the effect of further increasing the vapor pressure of the stream and is therefore not a viable route for using the stream in gasoline blending materials.
[0012] US Patent No. 3,960,978 describes metallized (cation exchanged) zeolites, such as ZSM-5 and ZSM-11, comprising metals such as Zn, Cr, Pt, Pd, Ni and Re, for example, in a process technology called M-Forming ™ (Chen et al., 1986). The general understanding is that ion exchange adds oligomerization capacity to aromatization functionality within the stated zeolite matrix and can allow the conversion of low molecular weight olefins, such as propylene, to oligomers and aromatics, to through the dehydrocyclization functionality of the catalyst. However, the US refinery industry has not widely used this technology, presumably as it is not economically favorable and / or technically impractical, unduly complex.
[0013] Catalyst applications that substantially involve crystalline zeolites are also known. For example, published US patent application Nos. 2010/0247391, 2010/0249474, 2010/0249480 and 2014/0024870, describe processes that use amorphous silicon alumina materials containing Group VIII and Group VIB metals for the production of C5 + oligomers.
[0014] In this context, it is clear that improved materials and methods are needed to produce more valuable hydrocarbon mixtures from such streams.
[0018] The present invention relates to materials and processes for preparing a composition comprising, for example, aliphatic, olefinic, cyclic and / or aromatic hydrocarbons of five or more carbon atoms per molecule.
[0019] In a non-limiting embodiment, the process comprises providing a first hydrocarbon mixture comprising isomers of hydrocarbons. The process further comprises providing a heterogeneous catalyst comprising pentasilzeolite; amorphous silica, amorphous alumina, or a combination of these; Zn and / or Cu; and at least an exchanged metal of the Group VII series (comprising manganese, technetium, rhenium, and bohrium) in a range from about 0.05% to about 6% by weight.
[0020] The first hydrocarbon mixture is then contacted with the heterogeneous catalyst to form a second hydrocarbon mixture comprising molecules having five or more carbon atoms.
[0021] In some non-limiting embodiments of any of the processes described in the present description, the process may further comprise stopping the formation of the second hydrocarbon mixture, isolating the heterogeneous catalyst, and regenerating the heterogeneous catalyst to remove carbonaceous deposits.
[0022] In some non-limiting embodiments of any of the processes described in the present disclosure, the processes may further comprise heating or transferring heat to the first hydrocarbon mixture using one or more cross exchangers.
[0023] In some non-limiting embodiments of any of the processes described in the present disclosure, the processes may further comprise the use of a sulfur extraction member.
[0024] In some non-limiting embodiments of any of the processes described in the present description, the first hydrocarbon mixture is obtained from direct distillation naphtha derived from a crude oil distillation unit or from a gasoline or a natural condensate.
[0025] In some non-limiting embodiments of any of the processes described in the present description, the processes further comprise providing a liquid petroleum gas (LPG) composition comprising C3 or C4 hydrocarbons, or combinations of these with the first hydrocarbon mixture. comprising C5 or C6 hydrocarbon isomers or combinations thereof.
[0026] In a non-limiting embodiment of any of the processes described in the present description, the present invention relates to a process for preparing a composition comprising straight chain, olefinic, cyclic and / or aromatic hydrocarbons of five or more carbon atoms per molecule according to Figure 1.
[0027] The processes of the present invention are useful for upgrading light naphtha into higher molecular weight paraffins, naphthenics, and aromatics. The resulting improved naphtha products produced by these processes are high octane and can be directly useful as a gasoline blending material or as a feed to an extraction process for aromatics production.
[0029] Figure 1 is a flow chart illustrating a non-limiting embodiment of naphtha conversion using a Multibed downflow reactor in accordance with the present invention.
[0032] This description relates to processes for preparing a composition comprising aliphatic, olefinic, cyclic, and / or aromatic hydrocarbons of five or more carbon atoms per molecule. In a non-limiting embodiment, the processes are to prepare a composition comprising aliphatic, olefinic, cyclic, and / or aromatic hydrocarbons of six or more carbon atoms per molecule. In a non-limiting embodiment, the processes are to prepare a composition comprising aliphatic, olefinic, cyclic, and / or aromatic hydrocarbons of seven or more carbon atoms per molecule. The processes of the present invention use a strong catalyst that can handle small amounts of sulfur, an economical choice of a fixed-bed reactor design that preferably includes at least two catalyst beds, and in some embodiments, the removal of sulfur. integrated via adsorbent to meet the latest gasoline sulfur level 3 specifications.
[0033] The processes of the present invention comprise providing a first hydrocarbon mixture comprising isomers of hydrocarbons. In a non-limiting embodiment, the first hydrocarbon mixture comprises isomers of hydrocarbons containing five to seven carbon atoms. In some non-limiting embodiments, the first hydrocarbon mixture is obtained from straight run naphtha derived from a crude oil distillation unit or from a gasoline or natural condensate.
[0034] The processes of the present invention further comprise providing a heterogeneous catalyst.
[0035] The heterogeneous catalyst comprises pentasyl zeolite. In a non-limiting embodiment, the pentasyl zeolite comprises crystalline aluminosilicate silica / alumina in a molar ratio of between about 15 and about 100. In a non-limiting embodiment, the pentasyl zeolite comprises ZSM5.
[0036] In a non-limiting embodiment, the pentasyl zeolite is included in the catalyst in a range from about 1% to about 99% by weight of the total catalyst. In a non-limiting embodiment, the pentasyl zeolite is included in the catalyst in a range from about 20 % to about 85 % by weight of the total catalyst. The heterogeneous catalyst further comprises amorphous silica, amorphous alumina, or a combination of these. In a non-limiting embodiment, the zeolite comprises a mixture of silica and alumina.
[0037] In a non-limiting embodiment, silica, alumina, or a combination of these is included in the catalyst in a range from about 1% to about 99% by weight of the total catalyst.
[0038] Furthermore, the heterogeneous catalyst comprises Zn, CU, or both. In a non-limiting embodiment, Zn, CU, or both are included in the catalyst in a range from about 0.05% to about 3% by weight of the total catalyst.
[0039] Furthermore, the heterogeneous catalyst comprises at least one exchanged metal from the Group VII series. In a non-limiting embodiment, at least one of the Group VII series metals exchanged to produce the heterogeneous catalyst is rhenium.
[0040] In a non-limiting embodiment, the metal is in the range of about 0.05% to about 6% by weight of the total catalyst.
[0041] In a non-limiting embodiment, the metal is in the range of about 0.5% to about 6% by weight.
[0042] In a non-limiting embodiment, the heterogeneous catalyst is sized to achieve a weight hourly space velocity in the range of about 0.01 / hour to about 100 / hour, where weight hourly space velocity is defined as supply mass flow in kg / h divided by the mass of the catalyst in kg.
[0043] In a non-limiting embodiment, the first hydrocarbon mixture is contacted with the heterogeneous catalyst at a temperature between approximately 200 ° C and 500 ° C, and at a pressure between 1 barA and 20 barA. Typically, the first hydrocarbon mixture is present as a gaseous stream when contacted with the catalyst.
[0044] In a non-limiting embodiment, the catalyst used within the process comprises zeolite ZSM-5 in concentrations between 20-85% by weight, Zn, Cu or both Zn and Cu at a concentration less than 3% by weight and an element of the Group VII at a concentration of less than 5% by weight, together with an amorphous binder comprising silica and / or alumina. This illustrative catalyst provides high pentane or hexane conversion under conditions between 200-400 ° C and at operating pressures below 30 barg.
[0045] In a non-limiting embodiment, the processes further comprise providing a dilution stream of the liquid petroleum gas (LPG) composition comprising three and / or four carbon atoms per molecule with the first hydrocarbon mixture.
[0046] The processes further comprise contacting the first hydrocarbon mixture with the heterogeneous catalyst to form a second hydrocarbon mixture. In a non-limiting embodiment, the second hydrocarbon mixture has a higher linear octane number. In a non-limiting embodiment, the second hydrocarbon mixture comprises hydrocarbons having five or more carbon atoms. In a non-limiting embodiment, the second hydrocarbon mixture comprises hydrocarbons having six or more carbon atoms. In a non-limiting embodiment, the second hydrocarbon mixture comprises hydrocarbons having seven or more carbon atoms.
[0047] As those skilled in the art will understand after reading this disclosure, in addition to higher linear octane numbers, engine octane units and / or research octane units can be routinely obtained.
[0048] In a non-limiting embodiment, the second hydrocarbon mixture has a higher linear octane unit or number and a lower vapor pressure compared to the first hydrocarbon mixture. In a non-limiting embodiment, the second hydrocarbon mixture has a higher octane unit of about 10 units. In a non-limiting embodiment, the second hydrocarbon mixture has a higher octane unit of about 15 units. In a non-limiting embodiment, the second hydrocarbon blend has a higher octane unit of about 20 units. In a non-limiting embodiment, the second hydrocarbon blend has a higher octane unit of about 25 units.
[0049] In a non-limiting embodiment, the heterogeneous catalyst is within one or more bed members. Preferably, as an economical choice, a fixed bed reactor design is used that includes at least two catalyst beds.
[0050] In a non-limiting embodiment, each bed member comprises one or more supply points for the first hydrocarbon mixture.
[0051] In a non-limiting embodiment, the first hydrocarbon mixture is contacted with the heterogeneous catalyst using a temperature control member to control the temperature of the first hydrocarbon mixture. In a non-limiting embodiment, the temperature control member is located at or around one or more supply points of the first hydrocarbon mixture.
[0052] In some non-limiting embodiments, the processes further comprise stopping the formation of the second hydrocarbon mixture by isolating the supply in the first hydrocarbon mixture from the heterogeneous catalyst. This is typically accomplished by means of one or more isolation valves in the supply line to the catalyst. The hydrocarbons that are present in the catalyst are removed using nitrogen and or steam before starting the regeneration process. The heterogeneous catalyst is regenerated to remove carbonaceous deposits. In a non-limiting embodiment, the catalyst temperature during regeneration is approximately 200 ° C to 700 ° C. In a non-limiting embodiment, regeneration comprises passing hot wet or dry nitrogen, air, or combinations of these over the heterogeneous catalyst. Typically, the catalyst is regenerated by passing a stream of hot gas through the catalyst for a period of between 1 hour and 10 days. Initially, the gas stream is hot nitrogen. Air is added to the nitrogen to provide an oxidant. The oxidant oxidizes carbonaceous materials that accumulate on the catalyst surface and affect its catalytic activity. The typical flow rate of nitrogen is 0.5-2 kg / h for each kg of catalyst. The air flow rate is adjusted to maintain an oxygen content in the supply stream between 1 and 20% v / v. Steam can be added to the regeneration gas stream to enhance the regeneration process. The temperature of the regeneration gas stream that is supplied to the catalyst is progressively increased during the regeneration process within the range of 200-700 ° C.
[0053] In a non-limiting embodiment, the heterogeneous catalyst is within one or more bed members. Preferably, as an economical choice, a fixed bed reactor design is used that includes at least two catalyst beds. In this non-limiting embodiment, hot wet or dry nitrogen, air or combinations thereof is supplied to each catalyst bed member in parallel through one or more supply points of the first hydrocarbon mixture. This non-limiting embodiment with at least two catalyst beds can be particularly useful, whereby one is running, while the other reactor is regenerating. These reactors are designed in such a way that any of them can be removed from the naphtha processing line and periodically regenerated using air and nitrogen.
[0054] In some non-limiting embodiments, the processes further comprise transferring heat using one or more cross exchangers or heating the first hydrocarbon mixture to a temperature between 250 and 500 ° C using one or more cross exchangers.
[0055] In some non-limiting embodiments, the processes further comprise obtaining a liquid, semi-liquid, gaseous or semi-gaseous mixture, isolated downstream of the at least one cross exchanger. The hydrocarbon liquid, which typically comprises straight chain, olefinic, cyclic and / or aromatic hydrocarbons of five, six, seven or more carbon atoms per molecule, is typically obtained by condensing any volatile components that are present in the second mixture of hydrocarbons, where such condensation occurs when the stream is cooled in a heat exchange or combination of heat exchangers. The liquids can also be made by contacting the second hydrocarbon mixture with an absorbent liquid such as a heavier hydrocarbon stream or an organic solvent stream. Contacting the second hydrocarbon stream with an absorbent liquid can also be used in conjunction with a series of heat exchange units.
[0056] In some non-limiting embodiments, the processes further comprise using a sulfur removal member, which is typically located downstream of the heterogeneous catalyst, in such a way as to remove sulfur from the second hydrocarbon mixture. In a non-limiting embodiment, the sulfur extraction member comprises an adsorbent. In a non-limiting embodiment, the adsorbent comprises metal oxide. In a non-limiting embodiment, the sulfur removal member is operated at a temperature capable of removing sulfur. In a non-limiting embodiment, the sulfur extraction member is operated at a temperature of between about 80 ° C to 200 ° C.
[0057] In some non-limiting embodiments, the second hydrocarbon mixture is isolated in a drum, absorption tower, or distillation column or combinations thereof.
[0058] In a non-limiting embodiment, the present invention provides a process solution for upgrading light naphtha feedstocks, such as straight run naphtha, or condensate, and converting them into higher boiling range naphtha with higher octane number or unit and lower vapor pressure, which can be useful as gasoline blending materials.
[0059] A process diagram for converting light naphtha to form a higher boiling range material containing aromatics is provided in Figure 1. The purpose of the process is to substantially convert light paraffinic compounds such as hexane and pentane, which they have a high proportion of straight chain isomers, in larger naphthenic, paraffinic and aromatic components, such that they can be used as high octane gasoline.
[0060] As shown in Figure 1, the light naphtha supply comprising, for example, pentane and hexane enters the process as a liquid in stream 101 . The remaining stream 102 is further divided into two streams 102 and 105 . Stream 102 is sent through exchangers and heaters prior to reaction. The cross exchanger 23 uses the effluent from the hot reactor to heat the cold input supply stream, stream 102 . Typical temperatures of about 150 to 300 ° C are achieved using the cross exchanger, resulting in stream 103 . Stream 103 is further heated to a reaction temperature of about 200 to 500 ° C using fire heater 21 . The hot gas supply 104 enters the top of reactor 22 and flows down where it is at least partially reacted on a 1st catalyst bed containing a zeolite catalyst. The supply from cooler 105 can be injected into the reactor to lower the temperature before being introduced into the second catalyst bed. The combined effluent from the 1st catalyst bed and the cooler supply injection 105 , if used, is further further reacted on a 2nd catalyst bed. The hot effluent from reactor 106 exits the reactor and is cooled using cross exchanger 23 . The cooled stream 107 is processed in an optional sulfur extraction bed 24 , which adsorbs the sulfur components. Desulfurized stream 108 is cooled in cooler 25 . The resulting product stream 109 , containing 2-phase liquid and vapor products, is separated in vessel 26 . Most of the methane and ethane, which are produced as by-products in reactor 22 , exit the process in stream 110 . The remaining stream is further processed in fractionation column 27 where LPG components such as propane and butane are removed as the top product 113 , while the enhanced naphtha in stream 114 is directed to the gasoline pool.
[0061] In a non-limiting embodiment, the present invention relates to a process according to Figure 1 for preparing a composition comprising straight chain, olefinic, cyclic and / or aromatic hydrocarbons of five, six, seven or more carbon atoms per molecule.
[0062] An alternative non-limiting embodiment of the naphtha upgrade process involves the co-injection of LPG comprising primarily butane or propane into stream 115 . An advantage of this process is that any olefin compounds present in LPG are converted to gasoline compounds. Additionally, the light olefinic material helps to initiate the enhancement reactions, increasing the octane content of the resulting naphtha.
[0063] The process flow diagram provided in the present description is a non-limiting illustration of the general process. Upon reading this description, the skilled person would understand that certain bypasses known to those skilled in the art may be used, such as, but not limited in any way to, further integration with conventional FCC light end recovery equipment, various thermal integration options and product stabilization process.
[0064] The following non-limiting examples are provided to further illustrate the present invention. A non-limiting example of a catalyst useful in conjunction with the illustrated process and comprising pentasyl zeolite in a range from about 1% to about 99%; amorphous silica, amorphous alumina, or a combination of these, ranging from about 1% to about 99%; Zn and / or Cu, in a range between about 0.05% to about 3% by weight; and at least one metal exchanged from the Group VII series in a range from about 0.05% to about 6% by weight is set forth in Example 1. The process performance of this catalyst is described by Examples 2, 3, 4 and 5.
[0066] Examples
[0068] Example 1: Catalyst
[0069] 75 grams of ZSM5 powder with a Si / Al ratio of 15/1 was mixed with 20 grams of kaolin, 5 grams of carboxymethylcellulose and enough water to form a paste suitable for extrusion after mixing in a high shear sigma sheet mixer . After extrusion through a 3mm trilobular geometry die plate extruder with multiple short L / D ratio, the green extrudate is dried at 120 ° C in air for 3 hours followed by calcination in air at 650- 750 ° C for 3 hours. After calcination, sodium exchange was performed with aqueous zinc, rhenium, and copper salts to achieve a metal loading of 1 weight percent for each metal, respectively. After ion exchange, the extrudate was air dried at 120 ° C for 3 hours followed by calcination at 650-750 ° C for 3 hours. After the final calcination, the catalyst was prepared for activity testing in a fixed bed reactor.
[0070] Example 2: Average catalyst performance of 12 hours, from a current time of 96-140 hours
[0071] 10 grams of 16 mesh particle size catalyst was loaded into a 0.500 inch diameter 316 SS reactor tube, equipped with a thermocouple, located in the middle of the catalyst bed, with glass beads above and below. Then, the reactor tube was placed in an electric tube furnace. The reactor tube was heated to 300 ° C under a constant flow of research grade nitrogen, while maintaining a back pressure of 9 barg.
[0072] Once the internal catalyst bed temperature stabilized at 300 ° C, the nitrogen supply was discontinued and the space velocity per hour by weight of 0.4 n-hexane was introduced to the reactor, while maintaining a back pressure of 9 barg . The catalyst bed temperature of 300 ° C was maintained for 24 hours under the constant supply of hydrocarbons; after which, it was increased to 350 ° C at a rate of 1 ° C / minute. The gaseous product stream was analyzed online by an Agilent 7890B gas chromatograph, while the liquid product stream was periodically analyzed offline by an Agilent 7890B gas chromatograph to confirm the production of C4 + and the supply conversion in the condensate. . Detailed hydrocarbon analysis was obtained using ASTM D6730 method. The average catalyst performance of 12 hours, from a current point of 96-140 hours is given in the table below.
[0074]
[0077] The C5 + product composition was measured in mass percent. This GC analysis was as follows:
[0079]
[0080] Example 3: Average catalyst performance of 10 hours from a time in the stream of 100-110 hours
[0081] The procedure of Example 2 was repeated for the catalyst of Example 1. The reactor was heated to 300 ° C, and the nitrogen supply was discontinued and the WHSV of 0.4 of an n-pentane was introduced at a back pressure of 9 barg. The reactor was slowly heated to 353 ° C and the conditions were held constant for 100 hours. The table below is the 10 hour average catalyst performance from a current time of 100-110 hours.
[0086] The composition of product C5 on a mass percent basis is as follows:
[0091] Example 4: Supply of mixed naphtha together with LPG diluent
[0092] A reactor operated with a supply of naphtha mixed together with LPG diluent. The reactor was operated at a temperature in the range 280-420 ° C, preferably 350 ° C and a pressure of 9 barg. The delivery speed was equivalent to one space speed. The average performance of the reactor under the above conditions was as follows:
[0095] Example 5: Supply of mixed naphtha together with LPG diluent and a sulfur extraction bed
[0096] A reactor is operated with a 10,000-12,000 kg / hr mixed naphtha supply containing 90 ppm sulfur, along with the 2000 kg / hr LPG diluent flow and a sulfur extraction bed comprising a metal oxide. The reactor is operated at a temperature in the range 280-420 ° C, preferably 320 ° C, and a pressure of 10 barg. The sulfur extraction bed is operated at a temperature of 160-180 ° C. The catalyst loading was equivalent to a space velocity of 0.8-1.0 / h. The average performance of the reactor under the above conditions was as follows:
[0101] Example 6: Average catalyst performance of 10 hours from a current time of 520-530 hours
[0102] The procedure of Example 2 was repeated for the catalyst of Example 1. The reactor was heated to 300 ° C, and the nitrogen supply was discontinued and the WHSV of 0.4 from a mixed alkane supply was introduced at a back pressure of 0.34 barg. The reactor was slowly heated to 353 ° C. The reactor was operated at a temperature in the range of 300-350 ° C for 520 hours. The reactor temperature was adjusted to 315 ° C and the conditions were kept constant. The table below is the 10 hour average catalyst performance from a current time of 520-530 hours. Supply composition:
[0104] n-hexane: 39% w / w
[0105] 2- methylpentane: 24.6% w / w
[0106] 3- methylpentane: 14.9% w / w
[0107] 2.2- dimethylbutane: 2.2% w / w
[0108] 2.3- dimethylbutane: 3.9% w / w
[0109] Methylcyclopentane: 9.9 % w / w
[0110] Cyclohexane: 5.5% w / w
[0115] The aromatics composition of the liquid product (C5 +) on a mass percent basis is as follows:

权利要求:
Claims (31)
[1]
A process for preparing a composition comprising aliphatic, olefinic, cyclic, and / or aromatic hydrocarbons of five or more carbon atoms per molecule; the process comprises:
(a) providing a first hydrocarbon mixture comprising isomers of hydrocarbons;
(b) providing a heterogeneous catalyst; the heterogeneous catalyst comprises:
(i) pentasyl-zeolite in a range from about 1% to about 99%;
(ii) amorphous silica, amorphous alumina, or a combination of these, ranging from about 1% to about 99%;
(iii) Zn and / or Cu, in a range between about 0.05% to about 3% by weight; Y
(iv) at least one exchanged metal from the Group VII series in a range from about 0.05% to about 6% by weight;
(c) contacting the first hydrocarbon mixture with the heterogeneous catalyst; Y
(d) forming a second hydrocarbon mixture comprising molecules having five or more carbon atoms, the second hydrocarbon mixture having a higher octane unit and / or a lower vapor pressure compared to the first hydrocarbon mixture.
[2]
The process of claim 1, characterized in that the second hydrocarbon mixture has a higher octane unit of about 10 to about 25 units.
[3]
3. The process of claim 2, characterized in that the second hydrocarbon mixture has a higher linear octane number.
[4]
4. The process of claim 1, further comprising:
stop the formation of the second hydrocarbon mixture;
isolate the heterogeneous catalyst; Y
regenerate the heterogeneous catalyst to remove carbonaceous deposits.
[5]
The process of claim 4, characterized in that the heterogeneous catalyst is at a temperature of about 200 ° C to 700 ° C during regeneration and the regeneration comprises passing hot wet or dry nitrogen, air or combinations of these over the heterogeneous catalyst .
[6]
6. The process of claim 1, characterized in that the heterogeneous catalyst is within one or more bed members.
[7]
The process of claim 6, characterized in that each bed member comprises one or more supply points for the first hydrocarbon mixture.
[8]
8. The process of claim 7, characterized in that hot wet or dry nitrogen, air, or combinations thereof is supplied to each catalyst bed member in parallel through one or more supply points of the first hydrocarbon mixture.
[9]
The process of claim 7, characterized in that contacting the first hydrocarbon mixture with the heterogeneous catalyst further comprises using a temperature control member to control the temperature of the first hydrocarbon mixture, wherein the member of Temperature control is located at or around the one or more supply points of the first hydrocarbon mixture.
[10]
The process of claim 1, further comprising: transferring heat using one or more cross exchangers or heating the first hydrocarbon mixture using one or more cross exchangers.
[11]
The process of claim 1, further comprising:
using a sulfur extraction member comprising an adsorbent; Y
operating the sulfur removal member at a temperature capable of removing sulfur.
[12]
12. The process of claim 11, characterized in that the adsorbent comprises a metal oxide.
[13]
The process of claim 1, further comprising: obtaining the first straight-run naphtha hydrocarbon mixture derived from a crude oil distillation unit or from a gasoline or a natural condensate.
[14]
The process of claim 1, characterized in that the pentasyl-zeolite comprises silica / crystalline aluminosilicate alumina in a molar ratio of between about 15 and about 100.
[15]
15. The process of claim 1, characterized in that the pentasilzeolite comprises ZSM5.
[16]
16. The process of claim 1, characterized in that at least one of the Group VII series metals exchanged to produce the heterogeneous catalyst is rhenium.
[17]
17. The process of claim 10, further comprising: obtaining a liquid, semi-liquid, gaseous or semi-gaseous mixture, characterized in that the liquid, semi-liquid, gaseous or semi-gaseous mixture is isolated downstream of the at least one cross exchanger.
[18]
18. The process of claim 16, further comprising isolating the second hydrocarbon mixture in a drum, absorption tower, or distillation column or combinations thereof.
[19]
19. The process of claim 1, further comprising: contacting the first hydrocarbon mixture with the heterogeneous catalyst in step (c) at a temperature of between about 200 ° C and 500 ° C.
[20]
20. The process of claim 1, characterized in that the heterogeneous catalyst is sized to achieve a weight hourly space velocity in the range of about 0.01 to about 100.
[21]
21. The process of claim 1, further comprising: providing a dilution stream of the liquid petroleum gas (LPG) composition comprising three and / or four carbon atoms per molecule.
[22]
22. A process for preparing a composition comprising aliphatic, olefinic, cyclic and / or aromatic hydrocarbons of five or more carbon atoms per molecule; the process comprises:
(a) providing a first hydrocarbon mixture comprising C5 or C6 hydrocarbon isomers or combinations thereof, and optionally a liquid petroleum gas (LPG) composition comprising C3 or C4 hydrocarbons, or combinations thereof; (b) providing a heterogeneous catalyst; the heterogeneous catalyst comprises:
(i) pentasyl-zeolite in a range from about 1% to about 99%;
(ii) amorphous silica, alumina, or a combination of these in a range from about 1% to about 99%;
(iii) Zn and / or Cu, in a range between about 0.05% to about 3% by weight; Y
(iv) at least one exchanged metal from the Group VII series in a range from about 0.05% to about 6% by weight;
(c) contacting the first hydrocarbon mixture with the heterogeneous catalyst; Y
(d) forming a second hydrocarbon mixture comprising molecules having five or more carbon atoms; the second hydrocarbon blend has a higher linear octane number and lower vapor pressure compared to the first hydrocarbon blend.
[23]
23. The process of claim 22, further comprising:
contacting the heterogeneous catalyst within one or more bed members.
[24]
24. The process of claim 23, characterized in that each bed member comprises one or more supply points of the first hydrocarbon mixture.
[25]
25. The process of claim 24, characterized in that contacting the first hydrocarbon mixture with the heterogeneous catalyst further comprises:
using a temperature control member to control the temperature of the first hydrocarbon mixture, wherein the temperature control member is located at or around at least one of one or more supply points of the first hydrocarbon mixture.
[26]
26. The process of claim 22, characterized in that the pentasyl-zeolite comprises silica / crystalline aluminosilicate alumina in a molar ratio of between about 15 and about 100.
[27]
27. The process of claim 22, characterized in that the pentasyl zeolite comprises ZSM5.
[28]
28. The process of claim 22, characterized in that at least one of the Group VII series metals exchanged to produce the heterogeneous catalyst is rhenium.
[29]
29. The process of claim 22, further comprising:
stop the formation of the second hydrocarbon mixture;
isolate the heterogeneous catalyst; Y
regenerate the heterogeneous catalyst to remove carbonaceous deposits,
characterized in that the heterogeneous catalyst is about 200 ° C to 700 ° C and
wherein regeneration comprises passing hot wet or dry nitrogen, air, or combinations of these over the heterogeneous catalyst.
[30]
30. The process of claim 29, characterized in that the hot wet or dry nitrogen, air or combinations thereof used to regenerate the heterogeneous catalyst is supplied to each catalyst bed member in parallel through the separate hydrocarbon supply points .
[31]
31. A process according to Figure 1 for preparing a composition comprising straight chain, olefinic, cyclic and / or aromatic hydrocarbons of seven or more carbon atoms per molecule.

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同族专利:

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公开号 | 公开日

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BR112020011769A2|2020-11-17|

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ES2782052B2|2021-02-08|

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US20210206703A1|2021-07-08|

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WO2019118825A1|2019-06-20|

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优先权:

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申请号 | 申请日 | 专利标题

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US201762599275P| true| 2017-12-15|2017-12-15|

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US201762608111P| true| 2017-12-20|2017-12-20|

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PCT/US2018/065641|WO2019118825A1|2017-12-15|2018-12-14|Processes for preparing hydrocarbon compositions|

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