巴西专利BR112017000472B1 process for preparing c2 and c3 hydrocarbons

专利PDF首页>>巴西专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
a feed stream comprising hydrogen and a gas selected from carbon monoxide, carbon dioxide or a combination thereof is converted into a product mixture containing a combination of hydrocarbons of two carbon atoms and three saturated and unsaturated carbon atoms via contact with a mixed catalyst comprising a mixed metal oxide catalyst selected from a copper oxide catalyst, copper oxide / zinc oxide, copper / alumina oxide, copper oxide / zinc oxide / alumina, a zinc oxide catalyst / chromium oxide or a combination thereof, in admixture with a molecular sieve catalyst having a type of cha, ae, ael, afi, bea or ddr structure or a combination of these molecular sieves. examples of molecular sieve catalysts include frog-34, frog-18, frog-5 and beta. the advantages include reduced production of c1 hydrocarbons, c4 hydrocarbons and higher, or both; long catalyst lives; desirable conversions; and desirable proportions of paraffins c2 and c3.
公开号:BR112017000472B1
申请号:R112017000472-0
申请日:2015-07-08
公开日:2020-12-29
发明作者:Adam Chojecki；Davy NIESKENS；Thomas Davidian；Peter E. Groenendijk；Matthijs Ruitenbeek；Barry B. Fish；Max M. Tirtowidjojo；Garmt R. Meima
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

[001] The present application claims the benefit of United States Patent Application Serial Number 62/023500, filed on July 11, 2014, entitled “CONVERSION OF SYNTHESIS GAS OVER HYBRID CATALYST,” which is incorporated herein by reference in its wholeness.
[002] This invention relates generally to a process for converting a feed stream comprising hydrogen and at least one gas selected from (1) carbon monoxide, (2) carbon dioxide or (3) a combination thereof, into a product mixture comprising a combination of two and three saturated and unsaturated hydrocarbons using a mixed catalyst.
[003] For a number of industrial applications a desirable starting material is a lower hydrocarbon including, in particular, C2 and C3 olefins and / or C2 and C3 paraffins which can then be converted into olefins for use in or as materials starting point for producing plastics, fuels and various chemicals downstream. These C2 and C3 materials can be saturated or unsaturated and, therefore, can include ethane, ethylene, propane and / or propylene. A variety of methods for producing these lower hydrocarbons have been developed, including oil cracking and various synthetic processes.
[004] Some of these synthetic processes begin with the use of a hybrid catalyst. Different types of catalysts were also explored, as well as different types of feed currents and proportions of the feed current components. Note that certain inconsistencies in reference to mixed metal oxide catalysts are found in the art and are attributable to potential variations as to the exact state (s) at the point of catalytic application, but the researchers agree that any metal such as, for example, copper (Cu), zinc (Zn), chromium (Cr) or zirconium (Zr), exist in a metal oxide catalyst mixed in a non-elemental oxidation state, in which this may or may not actually form an oxide, even if it is here designated for convenience as simply the metal itself. The researchers also agree that the designation of a specific oxide, for example, CuO, does not necessarily exclude the presence of an additional or different oxide from the given metal.
[005] For example, in Park, Y.-K .; Park, K.-C .; Ihm, S.- K., “Hydrocarbon synthesis through CO2 hydrogenation over CuZnOZrO2 / zeolite hybrid catalysts,” Catalysis Today 44 (1998) 165-173, a catalyst including Cu / ZnO / ZrO2 and a zeolite selected from ZSM-5, SAPO -34 and SAPO-5 are used to hydrogenate a mixture of carbon dioxide (CO2) and hydrogen (H2).
[006] United States Patent (US) 6,376,562 B1 (Ihm, et al.) Also describes the use of a hybrid catalyst including a methanol synthesis catalyst and a methanol conversion catalyst. The experiments show the conversion of CO2 into hydrocarbons using a combination of Cu / ZnO / ZrO2, either with SAPO-34 or SAPO-5, or with Cu / SAPO-34 or Cu / SAPO-5.
[007] Another example can be found in Fujiwara, M .; Ando, H .; Matsumoto, M .; Matsumura, Y .; Tanaka, M .; Souma, Y., “Hydrogenation of carbon dioxide over Fe-ZnO / zeolite composite catalysts,” Chemistry Letters 1995, 24 (9), 839- 840, where CO2 is hydrogenated over a combination of Fe-ZnO and HY zeolite. The reaction involves a reaction from methanol to gasoline.
[008] US Patent Application Publication 2008/0319245 A1 (Fujimoto et al.) Describes a process for producing liquefied petroleum gas (hydrocarbon containing propane or butane as a major component) from carbon monoxide (CO) and H2 with a catalyst comprising a methanol synthesis component and a zeolite component. A preferred methanol synthesis component is an olefin hydrogenation catalyst comprising a metal such as palladium (Pd) supported on a Zn-Cr based catalyst. The zeolite component can be a β-zeolite catalyst (supported on Pd).
[009] WO 2010/068364 A2 (Kibby, et al.) Describes a process for converting synthesis gas with a catalyst system comprising GaZSM-5 and ZnO-Cr2O3 to generate high octane hydrocarbons boiling in the gasoline range.
[010] US Patent 8,513,315 B2 (Kibby, et al.) Discloses injection of CO2 into the synthesis feed gas to reduce or eliminate CO2 production during isosynthesis on a hybrid catalyst combining ZnO-Cr2O3 and ZSM-5 . This produces high-boiling hydrocarbons in the gasoline range.
[011] Fujiwara, M .; Kieffer, R .; Ando, H .; Souma, Y., “Development of composite catalysts made of Cu-Zn-Cr oxide / zeolite for the hydrogenation of carbon dioxide,” Applied Catalysis A: General, 121 (1) (1995) 113-124 discloses CO2 hydrogenation over a hybrid catalyst comprising oxides of Cu-Zn-Cr and a zeolite type Y or H-ZSM-5 of aluminum. The results suggest that hydrocarbon synthesis and methanol decomposition are competitive.
[012] Fujiwara, M .; Ando, H .; Tanaka, M .; Souma, Y., “Hydrogenation of carbon dioxide over Cu-Zn-chromate / zeolite composite catalyst: The effects of reaction behavior of alkenes on hydrocarbon synthesis,” Applied Catalysis A: General 130 (1995) 105-116, reports the preparation of alkenes on a hybrid catalyst comprising non-calcined copper, zinc and chromium salts and HY zeolite.
[013] Fujimoto, K .; Shikada, T., “Selective synthesis of C2-C5 hydrocarbons from carbon dioxide using a hybrid catalyst composed of a MeOH synthesis catalyst and zeolite,” Applied Catalysis 31 (1987) 13-23, reports the preparation of hydrocarbons from a mixture of CO2, CO and H2 on a hybrid catalyst comprising oxides of copper and zinc, or oxides of zinc and chromium and a zeolite type Y of aluminum.
[014] Fujiwara, M .; Kieffer, R .; Ando, H .; Xu, Q .; Souma, Y., “Change of catalytic properties of FeZnO / zeolite composite catalyst in the hydrogenation of carbon dioxide,” Applied Catalysis A: General 154 (1-2) (1997), 87-101, reports hydrogenation of CO2 over a mixture of iron and zinc oxides, and a HY zeolite.
[015] Fujiwara, M .; Souma, Y., “Hydrocarbon synthesis from carbon dioxide and hydrogen over Cu-Zn-Cr oxide / zeolite hybrid catalysts,” Journal of the Chemical Society, Chemical Communications 10 (1992) 767-768, reports a combination of copper oxides, zinc and chromium and zeolites for hydrocarbon synthesis.
[016] Inui, T .; Kitagawa, K .; Takeguchi, T .; Hagiwara, T .; Makino, Y., “Hydrogenation of carbon dioxide to C1-C7 hydrocarbons via MeOH on composite catalysts,” Applied Catalysis A: General 94 (1993) 14, 51-55, discloses the use of a hybrid catalyst comprising CuCrZn or CuCrZnPdNa and ZSM - 5. The reported results show a wide distribution of products, ranging from C1-C7, and a high selectivity for methane (CH4).
[017] Inui, T .; Kitagawa, K .; Takeguchi, T .; Hagiwara, T .; Makino, Y., “Hydrogenation of carbon dioxide to C1-C7 hydrocarbons via MeOH on composite catalysts,” Applied Catalysis A: General 94 (1993) (1) 31-44, reports hydrocarbon synthesis of CO2 and H2 via methanol over a hybrid catalyst comprising H-ZSM-5 and a Cu-Cr-Zn-oxide modified by Pd-Na.
[018] Jeon, J.-K .; Jeong, K.-E .; Park, Y.-K .; Ihm, S.-K., “Selective synthesis of C3-C4 hydrocarbons through carbon dioxide hydrogenation on hybrid catalysts composed of a MeOH synthesis catalyst and SAPO,” Applied Catalysis A: General 124 (1995) 91-106, reports the use of a hybrid catalyst comprising Cu / ZnO / ZrO2 or Cu / ZnO / Al2O3 and a zeolite selected from ZSM-5, SAPO-5 and SAPO-44.
[019] Li, C .; Yuan, X .; Fujimoto, K., “Direct synthesis of LPG from carbon dioxide over hybrid catalysts comprising modified MeOH synthesis catalyst and β-type zeolite,” Applied Catalysis A: General 475 (2014) 155-160, reports production of C3 and C4 paraffins on more of a Zr modified CuZn catalyst in combination with a Pd modified Beta zeolite.
[020] Lunev, N.K .; Shmyrko, Y.I .; Pavlenko, N.V .; Norton, B., “Synthesis of iso-hydrocarbons mixture from CO2 and H2 on hybrid catalysts,” Applied Organometallic Chemistry 15 (2001) 99-104, reports the formation of hydrocarbons ranging from C2 to C15 and beyond on a hybrid catalyst comprising a mixed metal oxide promoted with K and a zeolite ZSM-11 doped with Fe.
[021] Chinese Patent Publication (CN) 103508828A (Qing-Jie Ge, et al.) Discloses the preparation of ethane and propane from synthesis gas via a single conversion step in the presence of a multifunctional catalyst. The multifunctional catalyst is a mixture of a hydrogenation catalyst of CO and a molecular sieve catalyst modified with, for example, palladium, platinum, ruthenium, rhodium, copper, iron, cobalt and / or manganese. The CO hydrogenation catalyst can be copper (II) oxide / zinc oxide / aluminum oxide (CuO / ZnO / Al2O3), copper / zirconium dioxide (Cu / ZrO2), zinc oxide / chromium oxide ( III) (ZnO / Cr2O3), palladium / zinc / chromium (III) oxide (Pd / ZnO / Cr2O3), and / or palladium / cerium (IV) oxide (Pd / CeO2). The pressure is 1-5 megapascals (MPa).
[022] US Patent 4,472,535 (Chang, et al.) Teaches the conversion of syngas to a hydrocarbon-only product with selectivity for ethane via the use of a catalyst comprising a zeolite (eg ZSM-5 and ZSM-11) and a metal component (for example, palladium, thorium, platinum, iridium, copper, manganese, cobalt, chromium, zinc, rhodium or aluminum) distributed within the zeolite pore structure.
[023] Japanese Patent Publication (JP) 2009195815 (Xiahong, et al.) Discloses a catalyst for manufacturing liquefied petroleum gas, in which propane or butane is the main product. The catalyst comprises a copper-zinc methanol synthesis catalyst and a metal modified zeolite containing palladium, copper, chromium, manganese and / or iron.
[024] US Patent Application Publication 2007/0244000 (Molinier, et al.) Discloses a process for producing an olefin product that involves converting synthesis gas into an intermediate composition that is predominantly methanol (MeOH) and dimethyl ether ( DME) using a catalyst including at least one metal oxide and at least one molecular sieve. The intermediate composition is then contacted with an olefin-forming catalyst to form the olefin product. Metal oxide can include copper, silver, zinc, boron, magnesium, aluminum, vanadium, chromium, manganese, gallium, palladium, osmium or zirconium. The molecular sieve can be, for example, MCM-22, MCM-36, MCM-49, MCM-68, SAPO-11, SAPO-31 or SAPO-41.
[025] Yoo, KS, et al., “Influence of solid acid catalyst on DME production directly from synthesis gas over the admixed catalyst of Cu / ZnO / Al2O3 and various SAPO catalysts,” Applied Catalysis A: General 330 (2007) 57 , 57- 62, discusses the use of Cu / Zn / Al2O3 (KATALCO ™ 33-5) and SAPO (for example, SAPO-5, SAPO-11 and SAPO-34) catalysts. Conditions for direct DME synthesis include a GHSV of 6000 milliliters per gram of catalyst * hour (mL / g-cat * h), 260 oC and 4.2 megapascals (MPa). These conditions are not shown to result in significant hydrocarbon production.
[026] Fujimoto, K., et al., “Synthesis gas conversion using mixed catalyst composed of CO reducing catalyst and solid acid, IV. Selective synthesis of C2, C3 and C4 paraffins from synthesis gas, ”Journal of Catalysis 94 (1985), 16-23, discloses the use of hybrid catalysts composed of a physically mixed methanol (Pd / SiO2) catalyst and type zeolites Y with favorable conditions including a temperature of 300 ° C to 350 ° C and a pressure of 1.0 megapascals (MPa) to 5.1 MPa.
[027] Zhang, Q., et al., “A highly stable and efficient catalyst for direct synthesis of LPG from syngas,” Catalysis Letters (July 2005), Vol. 102, Nos. 12, 51-55, discloses direct synthesis of liquefied petroleum gas (LPG) of synthesis gas on a hybrid catalyst containing a methanol synthesis catalyst (PdCa / SiO2) and a zeolite (β-zeδlite).
[028] Xiangang, M., et al., “Direct synthesis of LPG from syngas derived from air-POM,” Fuel 90 (2011), 2051-2054, deals with the use of synthesis gas derived from partial oxidation of CH4 with air (air-POM) using a hybrid catalyst consisting of a methanol and Y zeolite synthesis catalyst that has been modified with palladium.
[029] Zhang, Q., et al., “Synthesis of LPG from synthesis gas,” Fuel Processing Technology 85 (2004) 1139-1150, refers to the use of a hybrid catalyst consisting of a methanol synthesis catalyst and a zeolite in a fixed bed reactor to produce synthesis gas LPG. Methanol formed from synthesis gas on a methanol synthesis catalyst is first converted into DME and then into hydrocarbons over a zeolite. The hybrid catalyst discussed in this reference consists of USY zeolite and a copper / zinc oxide methanol synthesis catalyst.
[030] European Patent Application (EP) 2 055 380 A1 (Costa et al.) Relates to a process for producing hybrid catalysts for Fischer-Tropsch synthesis. The hybrid catalyst contains between 5 weight percent (weight percent) and 40 weight percent cobalt mixed with a bifunctional catalyst containing at least one Group VIB and / or Group VIII metal. The catalyst is transported on a support selected from zeolites, mesoporous silicoaluminates selected from structure types MOR, FAU, BEA, ITQ-2 and ITQ-6 and mixed acid oxides of the type WOx-ZrO2.
[031] Chen, Y., et al., “C2-C4 hydrocarbons synthesis from syngas over CuO-ZnO-Al2O3 / SAPO-34 bifunctional catalyst,” J. Chem. Technol. Biotechnol., January 9, 2014 (wileyonlinelibrary.com/jctb) DOI 10.1002 / jctb.4309 (8 pages), discloses synthesis gas hydrocarbon production on a bifunctional catalyst containing CuO / ZnO / Al2O3 and zeolite methanol synthesis catalyst SAPO-34. Production of C2-C4 hydrocarbons is balanced against coking via temperature change. Coking is shown after just 4 hours.
[032] Chen, Y., et al., “Synthesis of CuO — ZnO — Al2O3 with SAPO-34 core and shell structured catalyst by intermediate layer method,” Pure Appl. Chem. 2014, 86 (5), 775-783 discloses preparation of a layered structure to increase selectivity in CO hydrogenation to produce light hydrocarbons.
[033] Yu, Y., et al., “Transformation of syngas to light hydrocarbons over bifunctional CuO-ZnO / SAPO-34 catalysts: the effect of preparation methods,” Reaction Kinetics Mechanisms and Catalysis, April 26th 2014, 112, 489 -497, discloses a bifunctional catalyst including CuO / ZnO and SAPO-34 prepared by two different methods. Different methods are considered to have a significant effect on the performance of the catalyst, but the product obtained is not high in C2 and C3 paraffins.
[034] Despite obviously extensive research in this area, the problems commonly encountered include an unacceptable level of methanol remaining in the final product, an unacceptable level of methane, an unacceptable level of C4 and higher products, or a combination of these, requiring separations expensive to use C2 and C3 products effectively for their intended purposes. Thus, there remains a need in the art for processes that are effective for producing C2 and C3 products which also result in reduced amounts of methanol and / or C4 products and higher, but which still allow for desired levels of feed stream conversion. It is also desirable that a variety of feed streams can be used resulting in essentially the same product distribution, which reduces the feed stream purity requirements and / or the feed stream costs. It is also desirable that any (any) catalyst (s) have / will have desirably long lives under processing conditions. Finally, it is desirable that such a process minimizes or, preferably, does not involve the production of an intermediate product stream of methanol, DME or other oxygenates which would then be converted separately into the desired hydrocarbon product, that is, a C2 product and / or C3.
[035] In one embodiment the present invention provides a process for preparing C2 and C3 hydrocarbons comprising introducing a supply stream into a reactor, the supply stream comprising hydrogen gas (H2) and a gas selected from carbon monoxide (CO), carbon dioxide carbon (CO2) and combinations thereof, so that H2 gas is present in an amount of 10 percent by volume (% vol) at 90% vol, based on the combined volumes of H2 gas and the selected CO, CO2 gas and combinations thereof; and contacting the feed stream and a mixed catalyst in the reactor, the mixed catalyst comprising as components a mixed metal oxide catalyst selected from a copper oxide catalyst, a copper oxide / zinc oxide catalyst, an oxide catalyst copper / alumina, a copper oxide / zinc oxide / alumina catalyst, a chromium oxide / zinc oxide catalyst and combinations thereof; and a molecular sieve selected from molecular sieves having a structure type selected from CHA, AEI, AFI, AEL, BEA and DDR structure types, and combinations thereof; the types of structures corresponding to the International Zeolite Association naming convention; under reaction conditions sufficient to form a product mixture, the reaction conditions comprising a reactor temperature ranging from 300 degrees Celsius (oC) to 440 oC; a pressure of at least 1 bar (100 kilopascals, kPa); and an hourly space velocity of gas (GHSV) of at least 500 reciprocal hours (h-1); the product mixture having, as calculated on a CO-free, CO2-free, and H2-free basis, a combined ethane and propane content that is greater than 45 weight percent (% w); a methane content of less than 15% w; a higher combined butane and saturated hydrocarbon content of less than 30 wt%; and a combined unsaturated and oxygenated hydrocarbon content of less than 10 wt%; each weight percentage being based on the weight of the total product mixture and, when taken together, equaling 100% w.
[036] The above process is useful in that it converts a feed stream which comprises, consists essentially of, or consists of H2 gas and a gas selected from CO, CO2 or a combination thereof in a product mixture comprising a combination of hydrocarbons of two carbon atoms and three saturated and unsaturated carbon atoms, such as primarily C2 and C3 paraffins. The product mixture itself is useful as a cracker feed stream to produce certain olefins and / or as a starting or intermediate material to produce a range of chemicals including plastics, fuels and the like.
[037] It will be understood that CO or CO2 may each be present in the supply stream as a single second gas, or a combination of both may be present in any proportion with respect to each other. In other words, the feed stream may comprise, essentially consist of, or consist of, (1) a combination of CO and H2, or (2) a combination of CO2 and H2, or (3) a combination of (1) and (2) (this being a combination of CO, CO2, and H2) and regardless of which modality is employed, it will react according to the process conditions of the invention to form a combination of C2 and C3 products falling within the limitations of product mixture. In all cases the output stream may contain CO, CO2, and H2 originating from unconverted power components or from the Water Gas Displacement reaction or its reverse.
[038] Those skilled in the art, with minimal experimentation, will be able to confirm the desired balance between feed stream composition and C2 and C3 products and their proportions within the product mix limitations, as will be described here below.
[039] When more than 50 mol percent (mol%) of all carbon in the feed stream is initially in the form of CO, CO can be said to be the primary carbon-containing constituent of the feed stream. In preferred embodiments, that CO is present in an amount greater than 60 mol%, more preferably greater than 70 mol%, even more preferably greater than 80 mol% and more preferably greater than 90 mol%. H2 gas is measured separately and is desirably present in the supply stream in a volumetric ratio from H2 to CO (H2: CO) that is greater than or equal to 0.5: 1, preferably greater than or equal to 0.6: 1, more preferably greater than or equal to 1: 1, even more preferably greater than or equal to 2: 1, even more preferably less than or equal to 10: 1, still more preferably less than or equal to 7: 1, and finally, more preferably less than or equal to 3: 1 to 6: 1.
[040] When more than 50 mol% of all carbon in the feed stream is initially in the form of CO2, CO2 can be said to be the primary carbon-containing constituent of the feed stream. In preferred embodiments, that CO2 is present in an amount greater than 60 mol%, more preferably greater than 70 mol%, even more preferably greater than 80 mol% and more preferably desirably present in the feed stream in a volumetric ratio of H2 to CO2 ( H2: CO2) which is greater than or equal to 0.5: 1, preferably greater than or equal to 0.6: 1, more preferably greater than or equal to 1: 1, even more preferably greater than or equal to 2: 1, still more preferably less than or equal to 10: 1, even more preferably less than or equal to 9: 1, and finally, most preferably from 3: 1 to 8: 1.
[041] In the process of the present invention, the selected supply current is passed to a reactor via a heated reactor inlet and the typical reactor moves over and / or through a mixed catalyst bed under conditions sufficient to convert the gas containing carbon (CO, CO2, or a combination thereof) in the product mixture. The conditions under which this process can be carried out comprise, essentially consist of, or consist of: (1) a reactor temperature ranging from 300 oC to 440 oC; (2) a pressure of at least 1 bar (0.1 megapascals (MPa)); and (3) a GHSV of at least 500 h-1. As used herein, the phrase "reactor temperature" will be understood to represent either an average reactor temperature, where the temperature is measured in more than one location within the reactor, or the single temperature, where the temperature is measured in just one inside the reactor. However, those skilled in the art will recognize that the temperature at different locations within the reactor will almost certainly vary slightly, according to flow rates, catalyst flow and bed packaging, reactor size and geometry, variation in inlet temperatures in the reactor and so on, and will be able to easily adjust process parameters and other means to control the temperature, such as the use of a multi-tube heat exchanger, to ensure that the reactor temperature requirements of the present invention are met. attended.
[042] In certain particular embodiments, in which the primary carbon-containing constituent of the feed stream, as defined above, is CO, these reaction conditions preferably comprise, essentially consist of or consist of: (1) a reactor temperature varying 350 oC, more preferably 360 oC, and even more preferably 370 oC to 440 oC, more preferably 410 oC, and even more preferably 390 oC; (2) a pressure of at least 20 bar (2.0 MPa), more preferably at least 35 bar (3.5 MPa), and even more preferably at least 50 bar (5.0 MPa); and (3) a GHSV of 500 h-1, more preferably of 1000 h-1, and even more preferably of 3000 h-1, at 12000 h-1, more preferably at 10,000 h-1, and even more preferably at 6000 h-1.
[043] In other embodiments, where the feed stream comprises carbon which is predominantly, as defined above, in the form of CO2, such reaction conditions preferably comprise, consist essentially of, or consist of: (1) a temperature of reactor ranging from 300 oC, more preferably from 320 oC, and even more preferably from 330 oC to 400 oC, more preferably at 390 oC, and even more preferably at 380 oC; (2) a pressure of at least 2 bar (0.2 MPa), more preferably at least 28 bar (2.8 MPa), and even more preferably at least 40 bar (4.0 MPa); and (3) a GHSV of 500 h-1, more preferably of 1000 h-1, and even more preferably of 3000 h-1, at 22000 h-1, more preferably at 10,000 h-1, and even more preferably at 6000 h-1.
[044] The mixed catalyst bed comprises a mixed metal oxide catalyst which is a mixed metal oxide so-called "methanol synthesis catalyst," comprising, consisting of, or consisting essentially of a mixed metal oxide selected from copper oxide, copper oxide / zinc oxide, copper oxide / alumina, copper oxide / zinc oxide / alumina or chromium oxide / zinc oxide, in admixture with a molecular sieve catalyst selected from molecular sieves having a molecular sieve structure type selected from structure types CHA, AEI, AEL, AFI, BEA and DDR and combinations of such molecular sieves. Examples of these may include, but are not necessarily limited to, CHA = SAPO-34, AlPO-34, and SSZ-13; AEI = SAPO-37, SAPO-11, SAPO-18, AlPO-18, AlPO-11 and SAPO-31; AFI = SAPO-5; AEL = SAPO-11 and AlPO-11; BEA = Beta; and DDR = ZSM-58. As the term is used here, molecular sieves "SAPO" are defined as silicoaluminophosphate materials having a silicon content of at least 0.01% w, preferably at least 0.1% w and most preferably at least 0.5% for. Many of these materials will have a silicon content of at least 5% w or greater. Thus, based on this definition, molecular sieves that are mainly aluminophosphates, but actually contain very small amounts of silicon, ie less than 0.01% w, would still be classified as "AIPO" molecular sieves. The molecular sieves listed above include a variety of eight to twelve membered ring molecules of varying pore size, configuration and susceptibility to morphological change, but which are suitable, in combination with the enumerated mixed metal oxides and under reaction conditions defined, to form a mixture of products falling within the given description limitations. Combinations of molecular sieves having any of the above types of structures can also be employed.
[045] In especially preferred embodiments, the selected molecular sieve is modified by non-metal, that is, it does not include in its crystalline network any metal hetero atoms other than those of which the network as a whole is composed. Thus, for example only, a silicoaluminate, for example, a zeolite such as Beta, would not include any metal atom other than silicon and aluminum, and a silicoaluminophosphate, such as a FROG, would not include any metal atom other than silicon, aluminum. and phosphorus.
[046] With specific regard to SAPO silicoaluminophosphate molecular sieves, it will be understood by those skilled in the art that the elemental composition of the anhydrous form can be represented as (SixAlyPz) O2, where x, y and z represent molar fractions of silicon, aluminum and phosphorus, with x + y + z = 1. See, for example, Lok, BM, et al., “Silicoaluminophosphate Molecular Sieves: Another New Class of Microporous Crystalline Inorganic Solids,” J. Am. Chem. Soc. 106 (1984) 6092-6093. As noted above, the use of a combination of these metal oxides mixed in admixture with a molecular sieve is also acceptable and the mixed metal oxides can be made separately or together. The mixed metal oxide catalyst and the molecular sieve catalyst are preferably present in the reactor, typically as a mixed catalyst in a catalyst bed, in a weight / weight (w / w) ratio (mixed metal oxide catalyst: molecular sieve catalyst) ranging from 0.1: 1 to 10: 1, preferably from 0.5: 1 to 9: 1.
[047] In one embodiment, the mixed metal oxide catalyst is preferably a copper oxide catalyst, in which the copper content ranges from greater than 0% w to 90% w. In another embodiment, the mixed metal oxide catalyst is preferably a copper oxide / zinc oxide catalyst, where each copper and zinc content, independently, ranges from greater than 0% w to 90% w. In yet another embodiment, the mixed metal oxide catalyst is preferably a copper / alumina oxide catalyst, in which the copper content ranges from greater than 0% to 90% and the aluminum content ranges from greater than 0% to 55% p. In yet another embodiment, the mixed metal oxide catalyst is preferably a copper oxide / zinc oxide / alumina catalyst, with each copper and zinc content varying from more than 0% to 90% by weight content. aluminum ranges from greater than 0% to 55% p. In yet another embodiment, the mixed metal oxide catalyst is preferably a chromium oxide / zinc oxide catalyst, wherein each of the chromium and zinc contents, independently, ranges from greater than 0% w to 80% w. Each of the weight percentages in this paragraph is based on the combined weight percentages of all metals in the mixed metal oxide. The oxygen in each catalyst is therefore present in a determined amount by subtracting the sum of the% w of the component metals from 100% w.
[048] It is further noted that aluminum oxide, that is, alumina, can be in any phase or combination of phases. However, in some embodiments there may be a preference for the use of a gamma-alumina, or predominantly (more than 50% w / w) gamma-alumina, the weight percentage based on the total alumina. Other alumina phases, such as alpha-alumina, omega-alumina, eta-alumina, etc., can be used alternatively or as a component, preferably a minor component, with another alumina phase, such as a gamma phase.
[049] The product mixture resulting from the inventive process, following contact between the feed stream and the mixed catalyst under the specified reaction conditions, may desirably be high in saturated and unsaturated C2 and / or C3 products, such as ethane and / or propane and / or ethylene and / or propylene; relatively low in C1 products, such as CH4; and relatively low in oxygenated products. In particular modes, it is also relatively low on C4 and higher products. In general, the process shows improved selectivity of C2 and C3 paraffin products, that is, ethane and propane.
[050] More particularly, the product mixture, regardless of the precise composition of the feed stream within the given definition, can be characterized as having, as calculated on a CO free base, a CO2 free base and an H2 free base, a combined ethane and propane content that is greater than 45% w; a methane content of less than 15% w; a higher combined butane and saturated hydrocarbon content of less than 30 wt%; and a combined unsaturated and oxygenated hydrocarbon content of less than 10% w.
[051] In preferential modalities, and again, as calculated on a CO-free, CO2-free and H2-free basis, the combined ethane and propane content is greater than 60% w; the methane content is less than 10% w; the combined butane and highest saturated hydrocarbon content is less than 25 wt%; and the combined unsaturated and oxygenated hydrocarbon content is less than 5 p.
[052] In addition to the hydrocarbon values above, the output stream will obviously contain both the product mix and a certain proportion of unconverted gas selected from H2, CO, CO2, and combinations thereof, depending on the composition of the supply stream. The amount of each will vary according to a variety of factors well known to those skilled in the art, including carbon conversion, yield, catalyst productivity, time in the stream and so on. This stream of unconverted gas can be separated from the product mixture and, if desired, recycled back to the process again as a portion of the feed stream. Alternatively, it can be ventilated or otherwise disposed of with appropriate equipment, such as washers.
[053] EXAMPLE 1
[054] Physically mix 100 microliters (μL) of a mixed copper-zinc-aluminum metal oxide catalyst that has a copper (Cu) content of 39% w, a zinc (Zn) content of 25% w aluminum content (Al) of 10% w (HiFUEL ™ R120) and 100 microliters (μL) of a silicoaluminophosphate catalyst (SAPO-34) by shaking them together in a bottle. Each of the two catalysts has a particle size before mixing ranging from 40 mesh (0.422 millimeter (mm)) to 80 mesh (0.178 millimeter).
[055] Activate the catalyst physically mixed using a mixture 90/10% vol /% vol of H2 and nitrogen (N2) at a GHSV of 6000 h-1, a temperature of 280 ° C and a pressure of 10 bar (1, 0 MPa) over a period of three hours (3 h). Use the start of activation as a reference point for Time in Current (TOS) = 0 hour (h).
[056] Pass a combination of CO and H2 (H2: CO ratio of 1) over the activated catalyst at a GHSV of 6000 h-1 while maintaining pressure at 10 bar (1.0 MPa) and using a test protocol of varied sorting in H2: CO ratio and temperature (T) with a residence time for each 6h stage as follows: Table 1. Process conditions for CuO / ZnO / Al2O3 + SAPO-34 catalyst. Stage Ratio H2: CO (vol / vol) T (° C)

[057] The data in Table 2 below are (a) only for Stages 4 and 6; (b) based on the analysis of a sample of gaseous reactor effluent; and (c) determined using a calculation convention in which selectivity for each product is referenced only for detected products. Table 2. Results for CuO / ZnO / Al2O3 + SAPO-34 catalyst.
* Represents oxygenates and any hydrocarbons that are otherwise below the limit of quantification (BQL).
[058] Those skilled in the art recognize that converting a combination of CO and H2 can yield a number of unspecified by-products, including some that can be deposited in the catalyst bed (for example, as carbon or as waxes) and, as therefore, they cannot be detected by gas chromatography (GC). A conversion and selectivity calculation that appears to be more accurate references data to an absolute decrease in the amount of CO passing through the reactor (hereinafter referred to as "absolute carbon conversion" and "absolute carbon selectivity"). Table 3 below presents results recalculated for Stages 3 to 6 of the screening protocol above. The recalculated results reflect peak attribution corrections based on the use of a reference cylinder of known gas composition (a certified mixture of simple paraffins (lower hydrocarbons (C1-C6), without isomers, such as isobutane), olefins ( without isomers, such as 2-butene), CO, CO2 and H2 balanced at 100% vol by N2. The recalculation indicates that the olefins reported in Table 2 are not actually olefins and, therefore, their values in Table 3 are corrected to 0. Table 3. Results for recalculated CuO / ZnO / Al2O3 + SAPO-34 catalyst.

[059] The data in Table 3 demonstrates that the higher temperature shown (400 oC) improves the yield of C2-C3 hydrocarbons, increasing both CO conversion and C2-C3 selectivity. The data also demonstrate that, for the conditions shown in this Example 1, an increase in the H2: CO ratio, while maintaining the same temperature, pressure and GHSV, leads to an increase in CO conversion, but with a higher selectivity for CH4 . EXAMPLE 2
[060] Replicate Example 1, but use four stages instead of six stages, with an H2: CO ratio of 1, a process pressure of 10 bar (1.0 MPa), a 6000 h-1 and a time 6 h residency per internship. The results are recorded in Table 4 below. Table 4. Results for CuO / ZnO / Al2O3 + SAPO-34 catalyst.
* Outside the claimed temperature range. ** "Below the Quantitation Limit," an indication that with the GC apparatus used for this Example, a peak value is too small to be quantified.
[062] The data in Table 4 demonstrate that at a temperature beyond 360 oC it operates more effectively than a temperature of 360 oC or lower to reduce the formation of CH4 (C1 hydrocarbon), while improving the conversion of carbon and selectivity for products C2 and C3 according to the conditions previously defined in this Example 2. A comparison of these data with the data in Table 3 also shows that the overall selectivity for products C2 and C3 is higher at 380 oC, 10 bar pressure , and an H2: CO ratio of 1 than at 400 oC, 10 bar (1.0 MPa) pressure and an H2: CO ratio of 1. EXAMPLE 3
[063] Replicate Example 2, but introduce a combination of CO and H2 into the reactor only after the reactor temperature reaches a temperature of 380 oC. The results are reported in Table 5 below. Table 5. Results for CuO / ZnO / Al2O3 + SAPO-34 catalyst at 380 oC.

[064] A comparison of data from Tables 2-5 showing the results of catalytic performance for the same mixed ("hybrid") catalyst tested at pressure = 10 bar, GHSV = 6000 h-1 and H2: CO = 1 highlights a surprising and important effect on selectivity (less CH4 and more C2-C3 in the product stream) and activity (higher CO conversion), in which the hybrid is prevented from exposure to the reactive feed stream at lower process temperatures (below 360 oC). EXAMPLE 4
[065] Replicate Example 3, but with the same catalyst being exposed to a combination of CO and H2 that has an H2 ratio: CO = 3, pressure = 20 bar (2.0 MPa), reactor temperature of 380 oC, with a residence time of 12 h. The results are summarized in Table 6 below. Table 6. Results for CuO / ZnO / Al2O3 + SAPO-34 catalyst.

[066] The data in Table 6, in comparison with those in Table 5, demonstrate that the process conditions can be varied within the scope of the teachings presented here, while still obtaining significant improvement in carbon conversion, without appreciable differences in selectivity of C1- C4. EXAMPLE 5
[067] A comparison of the use of a CuO / ZnO / Cr2O3 + SAPO-34 catalyst versus a Cr2O3 / ZnO + SAPO-34 catalyst is performed to determine the CuO effect, as follows:
[068] Mixed Metal Oxide Catalyst (MMO) 5 (a): Prepare a mixed metal oxide catalyst from copper nitrate, zinc nitrate and chromium nitrate precursors. The target elemental composition is Cu (10 mol%), Zn (45 mol%) and chromium (Cr) (45 mol%).
[069] MMO catalyst 5 (b): Precursors are zinc nitrate and chromium nitrate. The target elemental composition is 50 mol% of Zn and Cr.
[070] Start the preparation of each catalyst by vigorously mixing solutions of the precursors added in a proportion that targets the desired elemental composition defined here above. Perform coprecipitation under ambient conditions (nominally 25 oC and one (1) atmosphere (atm, 1.01 bar, 98.1 kilopascals (kPa)) of pressure by transferring 20 milliliters (mL) of mixed precursor volume to a flask containing 20 mL ammonium hydroxide (Aldrich, 28-30% NH3 base). This results in a rapid coprecipitation of mixed hydroxides. During an accompanying aging phase (16 h), subject the coprecipitate to constant orbital agitation (500 revolutions per minute (rpm )) and heating (100 oC) to yield a gel-like residue of mixed hydroxides and oxides. Finally, transfer the residue to an oven and calcine it under programmed temperature conditions (static air, ramp 2 oC / min. up to 550 oC, residence 5 hours at 550 oC) Crush and sieve the calcined residue to a desired particle size (40 mesh (0.422 mm) to 80 mesh (0.178 mm)).
[071] X-ray fluorescence analysis of catalyst 5 (a) gives an elemental oxide composition as follows: CuO 8.9% w, ZnO 43.1% w and Cr2O3 48.0% w, each% being based on the combined weight of CuO, ZnO and Cr2O3. The X-ray fluorescence (XRF) analysis of catalyst 5 (b) gives an elemental oxide composition as follows: 51% wt ZnO and 49% wt Cr2O3 each% w being based on the combined weight of ZnO and Cr2O3 .
[072] Physically mix each catalyst independently (5 (a) or 5 (b)) with SAPO-34, as in Example 1, then activate the physical mixture as in Example 1, but change the reaction temperature to 400 oC and 450 oC, for physical mixtures SAPO-34/5 (a) and SAPO-34/5 (b), respectively, hereinafter referred to as hybrid catalysts HC-5a and HC-5b, respectively. The start of the activation stage is here a reference point for Time in Current (TOS) = 0 hour.
[073] Pass a combination of CO and H2 over the activated catalyst as in Example 1 using a process pressure (P) of 10 bar (1.0 MPa) and a temperature, GHSV and H2: CO ratio as shown in Table 7a (for HC-5a) and Table 7b (for HC-5b). Tables 8a, 8b and 8c show the conversion of CO and selectivity values for the given reactions. Table 7a. Conditions for HC-5a catalyst
* Outside the claimed temperature range. Table 7b. Conditions for HC-5b (Cr2O3 / ZnO catalyst + SAPO-34 catalyst)
* Outside the claimed temperature range. Table 8a. Stage 2 (400 ° C and H2: CO = 1) ratio for HC-5a, calculated using the same method as in Table 2.
* Conversion ** Selectivity Table 8b. HC-5a, corrected calculation using the same method as in Table 3.
* Outside the claimed temperature range Table 8c. HC-5b, calculated using the same method as in Table 4.
* Outside the claimed temperature range.
[074] The data in Tables 8b and 8c demonstrate that the mixed metal oxide catalyst based on chromium (Cr2O3 / ZnO, HC-5b) gives acceptable results when mixed with SAPO-34 at 400 ° C (Table 8c) , although its yield of C2 and C3 paraffins is less than that of the CuO / ZnO / Cr2O3 catalyst (HC-5-A) under similar conditions (Table 8b). Thus, the inclusion of CuO in the HC-5a catalyst offers a significant benefit. COMPARATIVE EXAMPLES A and B
[075] Replicate Example 1 with changes in temperature, pressure and GHSV as shown in Tables 9-A and 9-B below. Change the amount of HiFUEL ™ R120 and SAPO-34 to 500 μL for each catalyst and use a combination of CO and H2 having an H2: CO = 1 ratio. Tables 9-A and 9-B indicate the results of catalyst performance obtained during two separate tests, during which conditions are varied when the test proceeds.
[076] In the first test (Table 9-A for Comparative Example A), start exposing the activated catalyst to a combination of CO and H2 at a temperature of 280 ° C, pressure of 42 bar (4.2 megapascals (MPa )) and GHSV of 7200 h-1. As shown in Table 9-A, this combination of conditions yields a comparatively low conversion with no observed hydrocarbon production (only CO2 and oxygenates). In a second step, increase the temperature to 310 oC under the same conditions. In a third step, increase the temperature to 340 oC under the same conditions. In a fourth step, increase the temperature to 370 oC under the same conditions. In a fifth and last stage, increase the temperature to 400 oC under the same conditions.
[077] In the second test (Table 9-B for Comparative Example B), start exposing the activated catalyst to the combination of CO and H2 at a temperature of 340 ° C, and at the same pressure and GHSV as in the first test. In a second step, reduce the GHSV to 3600 h-1 under the same conditions. In a third step, decrease the pressure to 30 bar (3.0 MPa). In a fourth step, increase the temperature to 360 oC. In a fifth step, decrease the pressure to 20 bar (2.0 MPa). In a sixth and final stage, increase the temperature to 380 ° C. Table 9-A
* Outside the claimed temperature range. Table 9-B

[078] The data in Tables 9-A and 9-B show that a less preferred initial reactor temperature has an impact on the performance of the catalyst when the reactor is later brought into some of the more preferred temperature conditions. EXAMPLE 6
[079] Physically mixing a mixed copper-zinc-aluminum metal oxide catalyst having a copper (Cu) content of 39% w, a zinc (Zn) content of 25% w and an aluminum content of 10% w (HiFUEL ™ R120) and a silicoaluminophosphate catalyst (SAPO-34) by shaking them together in a bottle. Each of the catalysts has a particle size before mixing within a range of 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Activate the catalyst physically mixed with a stream of pure hydrogen at a flow of 100 milliliters per minute (mL / min.), A temperature of 270 oC and a pressure of 10 bar (1.0 MPa) for a period of 6 h. Pressurize the system with pure N2 to the desired operating pressure. Heat the system to the desired operating temperature while pure N2 gas is still flowing. Turn off the N2 flow and start passing the desired feed mixture over the activated catalyst.
[080] Tables 10-A1 to 10-F3 demonstrate how variations in a parameter, such as the temperature in Tables 10-A1 and 10-A2, affect CO conversion and product selectivity. Table 10-A1 - Temperature screening at a pressure of 20 bar (2.0 MPa), a 4000 h-1, an H2 / CO ratio of 3 and a HiFUEL R120 / SAPO-34 catalyst weight ratio of 3.
Comparative data Table 10-A2. (CO2-free selectivities and inclusive CO2 selectivities) Temperature screening at a pressure of 20 bar (2.0 MPa), a GHSV of 4000 h-1, an H2 / CO ratio of 3 and a weight ratio of catalyst HiFUEL R120 / SAPO-34 of 3

* Comparative data Table 10-B1. - Pressure screening at a temperature of 380 ° C, a GHSV of 4000 h-1, an H2 / CO ratio of 3, and a HiFUEL R120 / SAPO-34 catalyst weight ratio of 3
Table 10-B2. (CO2-free selectivities and inclusive CO2 selectivities) - Pressure screening at a temperature of 380 ° C, a GHSV of 4000 h-1, an H2 / CO ratio of 3 and a HiFUEL R120 / SAPO-34 ratio of 3
Table 10-C1. - Sorting the volumetric feed rate of H2 / CO at a temperature of 380 ° C, a pressure of 50 bar (5.0 MPa), a GHSV of 4000 h-1, an H2 / CO ratio of 3 and a ratio by weight of HiFUEL R120 / SAPO-34 catalyst of 3
Table 10-C2. (CO2-free selectivities and inclusive CO2 selectivities) - H2 / CO feed ratio screening at 380 ° C, 50 bar (5.0 MPa) pressure, 4000 h-1 GHSV, and a HiFUEL R120 / SAPO-34 catalyst weight ratio of 3
Table 10-D1. - Weight ratio (p) of HiFUEL R120 / SAPO-34 catalyst (sorting at a temperature of 380 ° C, GHSV of 4000 h-1, and an H2 / CO ratio of 3
Table 10-D2. (CO2-free selectivity and inclusive CO2 selectivity) - Pressure screening at a temperature of 380 ° C, GHSV of 4000 h-1, and an H2 / CO ratio of 3
Table 10-E1. - Sorting of GHSV at a temperature of 380 ° C, a pressure of 50 bar (5.0 MPa), an H2 / CO ratio of 3 and a HiFUEL R120 / SAPO-34 catalyst weight ratio of 3
Table 10-E2. - CO2 free selectivities and inclusive CO2 selectivities) - sorting of GHSV at a temperature of 380 ° C, a pressure of 50 bar (5000 kPa), an H2 / CO ratio of 3 and a weight ratio of HiFUEL catalyst R120 / SAPO-34 of 3
Table 10-F1. CO2-free coalimentation screening at a temperature of 380 ° C, a pressure of 40 bar (4.0 MPa), a volume ratio of H2 / CO of 3, a GHSV of 3,800 h-1, and a weight ratio of HiFUEL R120 / SAPO-34 catalyst of 3
Table 10-F2. (CO2-free selectivities and inclusive CO2 selectivity) - CO2 coalescing screening at a temperature of 380 ° C, a pressure of 40 bar (4000 kPa), an H2 / CO volume ratio of 3 to a 3,800 h GHSV -1 and a HiFUEL R120 / SAPO-34 catalyst weight ratio of 3

[081] The data presented in Tables 10-A to 10-F demonstrate first that, in certain embodiments, the invention may lead to the production of a combination of two carbon atoms and three saturated and unsaturated carbon atoms selected from ethane, ethylene, propane and propylene. Operation outside the parameters of the present invention can lead to the production of oxygenates at temperatures below 350 oC in long TOS (see Table 10-A1 comparative data). Second, an increase in pressure within the ranges shown in the Examples leads to an increase in CO conversion. For example, Table 10-B shows that at 20 bar (2.0 MPa) and above, there is more than ten times the conversion that occurs at 5 bar (0.5 MPa), while the highest pressure, such as 35 bar (3.5 MPa), the catalyst performance improves with TOS. Third, a certain minimum H2: CO ratio is desirable for long-term performance, with greater H2: CO ratios tending to favor a reduction in CO2 selectivity as shown in Table 10-C, where better catalyst stability is observed with an H2: CO ratio of 3 or higher. Table 10-D also shows that at a catalyst ratio (HiFUELTM R120 / SAPO-34) of 3 or less, better catalyst stability and productivity are observed. Fourth, within certain limits, higher GHSV rates can lead to catalyst deactivation faster than lower GHSV rates. For example, Table 10-E shows that, at a GHSV below 10,000 h-1, the performance of the catalyst is observed to be more stable than the higher GHSV. Fifth, the use of a CO2 coalimentation can lead to a reduction in the selectivity of liquid CO2, as shown in Table 4-F1, in which the selectivity of liquid CO2 drops from 42.9% to 13.6% when the amount of CO2 in the feed stream increases from 0 percent by volume (% vol) to 20% vol. EXAMPLE 7
[082] Physically mixing 1 gram (g) of a mixed copper-zinc-aluminum metal oxide catalyst having a copper (Cu) content of 39% w, a zinc (Zn) content of 25% w and a content 10% aluminum foil (HiFUEL ™ R120) with 0.33 grams of a silicoaluminophosphate catalyst (SAPO-34) shaking them together in a bottle. Each of the catalysts has a particle size before mixing within a range of 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Activate the physically mixed catalyst using a stream of pure hydrogen at a flow of 100 milliliters per minute (mL / min.), A temperature of 270 oC and a pressure of 10 bar (1.0 MPa) for a period of 6 h. Pressurize the system with pure nitrogen (N2) up to 40 bar (4.0 MPa). Heat the system to 400 oC while still flowing pure nitrogen. Pass 22.5 mL / min. of CO2, 67.5 mL / min of H2 and 10 mL / min. of N2 on the activated catalyst. Keep the temperature for 24 hours. Then, reduce the temperature by 25 oC and keep again for 24 h. Repeat at a temperature of 300 oC to be obtained. The results are recorded in Table 11.
[083] The catalyst is loaded only once, before Passage 1, for Passages 1-5, and no refilling is done. All pressure conditions, W / F and H2: CO2 ratios are consistent for these passages, with only the temperature changed. New catalyst is loaded for each of Passages 6-14 and pressure, W / F, H2: CO2 ratio or MMO / SAPO-34 weight ratios are changed as shown in Table 12. This Example 6 shows that, despite the changes in the parameters, a product mixture falling within the definition of Claim 1 can be obtained, although the exact quantities of products that C1, C2 and C3 are little changed. Passages 9, 10 and 14 in Table 11 provide examples of optimized reaction conditions, resulting in higher production of C2 and C3 paraffins. Table 11. Screening data from Example 7 for CuO / ZnO / Al2O3 + SAPO-34 catalyst and CO2 + H2 supply with temperatures, pressures, H2 / CO2 ratios, W / F and MMO / SAPO ratios.

[084] The extent of the reaction is calculated as the conversion of COX, where the reaction of CO2 to CO does not contribute to the conversion calculation. Table 12. Screening of Example 7 data reported as% by weight of output excluding CO, CO2 and H2.

[085] As noted in Table 11, the extent of the reaction is calculated as the COX conversion, where the CO2 to CO reaction does not contribute to the conversion calculation. COMPARATIVE EXAMPLE C
[086] Two embodiments of the inventive catalyst system are tested against a catalyst system as described in Park, Y.-K .; Park, K.-C .; Ihm, S.-K., “Hydrocarbon synthesis through CO2 hydrogenation over CuZnOZrO2 / zeolite hybrid catalysts,” Catalysis Today 44 (1998) 165-173, hereinafter "Parque", in a hydrogenation of CO2. Two separate mixed catalyst beds made up of the components for each catalyst, as shown in Table 13, are prepared, wherein the weight ratio of the mixed metal oxide to the zeolite component is 1: 1. A mixed flow of hydrogen and carbon dioxide, in a 3: 1 volumetric H2: CO2 ratio, is drained through each catalyst bed at a pressure of 28 bar (2.8 MPa); a temperature of 400oC; and one g of catalyst per flow rate of 20 g-cat h / mol. The products produced and their weight percentages based on 100 percent weight are shown in Table 13. Table 13. Hydrogenation of CO2 over hybrid catalysts, Parque data only.
Catalyst Park
[087] Table 13 shows that, for the Park process, the yield of C2 and C3 hydrocarbons is 10.7% by weight ((34.2 + 53.1) / 100 • 12.2% by weight = 10 , 7% by weight) and the CH4 yield is 0.3% by weight (2.1 / 100 • 12.2% by weight = 0.3% by weight).
[088] The Park data is then used to compare the catalyst system of the invention with the Park catalyst system, under the conditions employed in Park, including temperature (400oC), pressure (28 bar, 2.8 MPa), catalyst by weight per flow rate (W / F) of 20 g- cat * h / mol, volumetric ratio H2: CO2 of 3, and a ratio of mixed metal oxide catalyst to molecular sieve catalyst of 1: 1 on a base weight / weight. The results are shown in Table 14. Table 14. Comparison of yields using Park and Example catalysts under Park conditions.
1 Park Catalyst 2 * Example Catalyst. EXAMPLE 8
[089] A mixed catalyst comprising CuO / ZnO / Al2O3 is employed in a reaction to show the change in yields and improvement in yield of C2 and C3 attributable to the use of conditions including a temperature of 350oC, a pressure of 40 bar (4 MPa) , a weight to flow ratio (W / F) of 19.6 g-cat * h / mol, a H2: CO2 ratio of 10: 1, and a mixed metal oxide catalyst weight / weight ratio of 3 :1. The results are shown in Table 15. Table 15. Hydrocarbon yields under given conditions.
** Example Catalyst
[090] This Example 8 shows that the example catalyst, under the claimed process conditions, shows better performance than the Park catalyst under Park conditions. EXAMPLE 9
[091] A Cr2O3 / ZnO catalyst is prepared as follows:
[092] A 0.14 molar (M) cation solution is prepared by adding suitable amounts (targeting a 0.4: 1 Cr to Zn molar ratio) of Cr (NO3) 39H2O and Zn (NO3) 23H2O to distilled water (H2O). In addition, a 0.5 M (NH4) 2CO3 solution is prepared as a precipitating agent. The cation (Cr3 + / Zn2 +) and anion ((CO3) 2-) solutions are added simultaneously dropwise to a stirred beaker of distilled H2O kept at 7.0 <= pH <= 7.5 and T = 338 + / - 5 K. Coprecipitated materials are filtered, washed repeatedly with distilled water, dried in static air at 383 K and subsequently calcined at 873 K for 2 h.
[093] The prepared Cr2O3 / ZnO catalyst is then physically mixed with a silicoaluminophosphate catalyst (SAPO-34) taking appropriate amounts to achieve the weight ratio as indicated in Table 16 below and shaking them together in a bottle . Each of the catalysts has a particle size before mixing within a range of 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Pressurize the system with pure N2 to the value as indicated in Table 15. Heat the system to the value as indicated in Table 16, while still flowing pure N2. Turn off the nitrogen flow and start to pass a certain amount of CO, H2 and He over the catalyst to reach the feed rate and GHSV as indicated in the table. The results are shown in Table 16.
[094] Table 16. Screening of Cr2O3 / ZnO + SAPO-34 catalyst at varying pressures, catalyst ratios and GHSVs.
EXAMPLE 10
[095] Replicate Example 6, but change the type of catalyst in a first pass to a mixture of CuO / ZnO / Al2O3 and a combination of molecular sieve catalysts comprised of 75% by weight of SAPO-5 and 25% by weight of SAPO-34.
[096] In a second pass, change the type of catalyst to a mixture of CuO / ZnO / Al2O3 and SAPO-18.
[097] For a third pass, physically mix 50 microliters (μL) of a mixed metal oxide catalyst of CuO / ZnO / Al2O3 that has a Cu content of 39% by weight, a Zn content of 25% by weight and a 10 wt% Al content (HiFUEL ™ R120) with 150 μL of a H-Beta zeolite (ZEOCATTM PB / H ratio, SiO2 / Al2O3 = 24, available from Zeochem AG, Switzerland), shake them together in a bottle.
[098] Each of the catalysts has a particle size before mixing ranging from 40 mesh (0.422 mm) to 80 mesh (0.178 mm). For the first and second passages, activate the catalyst mixed physically according to Example 6. For the third pass, activate the catalyst mixed physically using a mixture of H2 and He and at a ratio of 90:10% vol /% vol at a GHSV of 2400 h-1, a temperature of 300 ° C and a pressure of 3 bar (0.3 MPa) for a period of 6 h.
[099] Pass a mixture of H2 and CO, volumetric ratio H2: CO = 3, over each activated catalyst under the conditions shown in Table 17. Table 18 illustrates the corresponding% p of the output, excluding CO2, CO and H2, for each one of the three catalyst passages. Table 17. Comparison of different molecular sieve catalysts for CO conversion.
Table 18.% w of output corresponding to the use of different molecular sieve catalysts.

权利要求:
Claims (10)
[0001]
1. Process for preparing C2 and C3 hydrocarbons, characterized by the fact that it comprises: (a) introducing a supply stream into a reactor, the supply stream comprising hydrogen gas and a gas selected from carbon monoxide, carbon dioxide and combinations thereof , so that H2 gas is present in an amount of 10 percent by volume to 90 percent by volume, based on combined volumes of hydrogen gas and the selected gas of carbon monoxide, carbon dioxide and combinations thereof; and (b) contacting the supply stream and a mixed catalyst in the reactor, the mixed catalyst comprising as components: (1) a mixed metal oxide catalyst selected from: a copper oxide catalyst, a copper / oxide catalyst zinc, a copper oxide / alumina catalyst, a copper oxide / zinc oxide / alumina catalyst, a chromium oxide / zinc oxide catalyst, and combinations thereof; and (2) a non-metal modified molecular sieve catalyst selected from SAPO-34, SSZ-13, SAPO-18, SAPO-5, SAPO-11, Beta-zeolite, ZSM-58 and combinations thereof; the types of structure corresponding to the International Zeolite Association naming convention; under reaction conditions sufficient to form a product mixture, the reaction conditions comprising: a reactor temperature ranging from 300 degrees Celsius to 440 degrees Celsius; a pressure of at least one bar (100 kilopascals); and an hourly space velocity of gas of at least 500 reciprocal hours; the product mixture having, as calculated on a carbon monoxide free, carbon dioxide free and hydrogen free basis, a combined ethane and propane content that is greater than 45 weight percent; a methane content of less than 15 weight percent; a higher combined butane and saturated hydrocarbon content of less than 30 weight percent; and a combined unsaturated and oxygenated hydrocarbon content of less than 10 weight percent; each weight percentage being based on the weight of the total product mix and, when taken together, equaling 100 percent by weight
[0002]
2. Process according to claim 1, characterized in that: the feed stream comprises carbon in the form of carbon monoxide in an amount greater than 50 mol percent, based on the total carbon in the feed stream; the volumetric ratio of hydrogen gas to carbon monoxide varies from 0.1: 1 to 10: 1; the mixed metal oxide catalyst is a copper oxide / zinc oxide / alumina catalyst; and the molecular sieve catalyst is SAPO-34.
[0003]
3. Process according to claim 1, characterized by the fact that: the feed stream comprises carbon in the form of carbon monoxide in an amount greater than 50 mol percent, based on the total carbon in the feed stream; the volumetric ratio of hydrogen gas to carbon monoxide varies from 0.1: 1 to 10: 1; the mixed metal oxide catalyst is a chromium oxide / zinc oxide catalyst; and the molecular sieve catalyst is SAPO-34.
[0004]
4. Process, according to claims 1, characterized by the fact that: the temperature varies from 350oC to 440oC; the pressure is at least 20 bar (2.0 megapascals); and the hourly space velocity of gas ranges from 500 reciprocal hours to 12000 reciprocal hours.
[0005]
5. Process according to claim 1, characterized by the fact that: the feed stream comprises carbon in the form of carbon dioxide in an amount greater than 50 mol percent, based on the total carbon in the feed stream; the volumetric ratio of hydrogen gas to carbon dioxide varies from 0.1: 1 to 10: 1; the mixed metal oxide catalyst is a copper oxide / zinc oxide / alumina catalyst; and the molecular sieve catalyst is SAPO-34.
[0006]
6. Process according to claim 1, characterized by the fact that: the feed stream comprises carbon in the form of carbon dioxide in an amount greater than 50 mol percent, based on the total carbon in the feed stream; the volumetric ratio of hydrogen gas to carbon dioxide varies from 0.1: 1 to 10: 1; the mixed metal oxide catalyst is a chromium oxide / zinc oxide catalyst; and the molecular sieve catalyst is SAPO-34.
[0007]
7. Process, according to claim 5, characterized by the fact that: the temperature varies from 300oC to 400oC; the pressure is at least 2 bar (0.2 megapascals); and the hourly space velocity of gas ranges from 500 reciprocal hours to 22000 reciprocal hours.
[0008]
8. Process according to claim 1, characterized in that: the mixed catalyst has a weight / weight ratio of mixed metal oxide catalyst to molecular sieve catalyst ranging from 0.1: 1 to 10: 1.
[0009]
9. Process according to claims 1, characterized by the fact that: the product mixture has, as calculated on a carbon monoxide free, carbon dioxide free and hydrogen free base, a combined ethane and propane content that it is greater than 60 percent by weight; a methane content of less than 10 weight percent; a higher combined butane and saturated hydrocarbon content of less than 25 weight percent; and a combined unsaturated and oxygenated hydrocarbon content of less than 5 weight percent; each weight percentage being based on the weight of the total product mixture and, when taken together, equaling 100 percent by weight.
[0010]
10. Process according to claim 1, characterized in that it consists of: (1) a mixed metal oxide catalyst selected from: a copper oxide catalyst, a copper oxide / zinc oxide catalyst, a catalyst copper oxide / alumina, a copper oxide / zinc oxide / alumina catalyst, a chromium oxide / zinc oxide catalyst, and combinations thereof; and (2) a non-metal modified molecular sieve catalyst selected from SAPO-34, SSZ-13, SAPO-18, SAPO-5, SAPO-11, Beta-zeolite, ZSM-58 and combinations thereof; the types of structure corresponding to the International Zeolite Association naming convention.

类似技术:

公开号 | 公开日 | 专利标题

BR112017000472B1|2020-12-29|process for preparing c2 and c3 hydrocarbons

JP5658562B2|2015-01-28|Catalyst composition and process for converting aliphatic fuel promoters to aromatic compounds

US4801573A|1989-01-31|Catalyst for production of hydrocarbons

EP2834210B1|2018-07-18|Process for the production of xylenes and light olefins from heavy aromatics

EP3368499B1|2019-08-07|Process to convert synthesis gas to olefins over a bifunctional chromium oxide/zinc oxide-sapo-34 catalyst

US9221037B2|2015-12-29|Multimetal zeolites based catalyst for transalkylation of heavy reformate to produce xylenes and petrochemical feedstocks

CN1732137A|2006-02-08|Linear alpha olefins from natural gas-derived synthesis gas over a nonshifting cobalt catalyst

Nieskens et al.2017|Production of light hydrocarbons from syngas using a hybrid catalyst

US4579830A|1986-04-01|Enhanced catalyst for converting synthesis gas to liquid motor fuels

BR112019015047A2|2020-03-03|PROCESSES TO IMPROVE THE ACTIVITY OF HYBRID CATALYSTS FOR FISCHER-TROPSCH REACTIONS

BR112019011997A2|2020-01-28|process for converting synthesis gas to olefins using a bifunctional chromium / zinc oxide catalyst - toad-34

EP0153517A1|1985-09-04|Novel catalysts and their preparation and process for the production of liquid paraffins

EP3052461A1|2016-08-10|Methanol conversion process

CN110036094A|2019-07-19|Comprehensive oxygenate conversion and olefin oligomerization

Magomedova et al.2017|Effect of feedstock and gas atmosphere composition on selectivity and distribution of hydrocarbon groups in gasoline synthesis from oxygenates

US4504590A|1985-03-12|Catalysts and their preparation

CA3125128A1|2020-07-02|Methods for producing c2 to c5 paraffins using a hybrid catalyst comprising gallium metal oxide

WO2020236431A1|2020-11-26|Methods for producing c2 to c5 paraffins using a hybrid catalyst comprising a high acidity microporous component

BR112021005088A2|2021-06-08|process for preparing c2 to c5 hydrocarbons.

WO2021136741A1|2021-07-08|Methods and systems for conversion of a paraffinic feedstock having increased isomerization

Vytnova et al.2006|Fischer-Tropsch synthesis on aluminum oxide-and zeolite-diluted catalysts

EP2699349A1|2014-02-26|Catalyst for use in production of saturated hydrocarbons from synthesis gas

CA3125122A1|2020-07-02|Catalysts comprising a zirconia and gallium oxide component for production of c2 to c4 olefins

CN110023458A|2019-07-16|For producing combination alkene and the oxygenate conversion of aromatic hydrocarbons

Lapidus et al.2007|Hydrocarbon synthesis from CO and H2: Promotion of Co/Al2O3 catalysts with noble metals

同族专利:

公开号 | 公开日

CN106660894A|2017-05-10|

ES2851874T3|2021-09-09|

CN106660894B|2019-09-03|

SA517380701B1|2020-08-18|

BR112017000472A2|2017-11-07|

EP3166912A1|2017-05-17|

WO2016007607A1|2016-01-14|

PT3166912T|2021-02-16|

CA2954285A1|2016-01-14|

US20170210679A1|2017-07-27|

US9919981B2|2018-03-20|

ZA201700625B|2018-08-29|

EP3166912B1|2020-12-02|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US4472535A|1982-11-22|1984-09-18|Mobil Oil Corporation|Conversion of synthesis gas to ethane|

KR100293531B1|1998-12-24|2001-10-26|윤덕용|Hybrid Catalysts for Hydrocarbon Generation from Carbon Dioxide|

US7492841B2|2003-01-30|2009-02-17|Andrew Corporation|Relative phase/amplitude detection system|

JP4965258B2|2004-08-10|2012-07-04|日本ガス合成株式会社|Catalyst for producing liquefied petroleum gas, and method for producing liquefied petroleum gas using the catalyst|

US20070244000A1|2006-04-13|2007-10-18|Michel Molinier|Producing olefin product from syngas|

JP2009195815A|2008-02-20|2009-09-03|Nippon Gas Gosei Kk|Catalyst for liquefied petroleum gas production and method for manufacturing liquefied petroleum gas using the same|

US7943673B2|2008-12-10|2011-05-17|Chevron U.S.A. Inc.|Process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system|

US8513315B2|2009-12-30|2013-08-20|Chevron U.S.A. Inc.|CO2 injection into synthesis feed gas to reduce or eliminate net CO2 production during isosynthesis over ZnO-Cr2O3 plus ZSM-5 hybrid catalyst combinations|

WO2012142727A1|2011-04-21|2012-10-26|Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences|Catalyst for use in production of saturated hydrocarbons from synthesis gas|

CN103508828A|2012-06-30|2014-01-15|中国科学院大连化学物理研究所|Method used for preparing ethane and propane from synthetic gas|

CN103772087B|2012-10-25|2016-12-21|中国石油化工股份有限公司|The method of the direct preparing low-carbon olefins of synthesis gas|

CN103071528A|2013-01-21|2013-05-01|浙江大学|Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method|WO2018004993A1|2016-07-01|2018-01-04|Res Usa, Llc|Reduction of greenhouse gas emission|

US9938217B2|2016-07-01|2018-04-10|Res Usa, Llc|Fluidized bed membrane reactor|

WO2018004992A1|2016-07-01|2018-01-04|Res Usa, Llc|Conversion of methane to dimethyl ether|

WO2018051198A1|2016-07-25|2018-03-22|Sabic Global Technologies B.V.|Process for high-pressure hydrogenation of carbon dioxide to syngas and methane using copper-manganese-aluminum mixed metal oxide catalysts|

AR110129A1|2016-11-16|2019-02-27|Dow Global Technologies Llc|PROCESSES AND SYSTEMS TO OBTAIN HIGH CARBON CONVERSION TO DESIRED PRODUCTS IN A HYBRID CATALYST SYSTEM|

CN108144643B|2016-12-05|2020-03-10|中国科学院大连化学物理研究所|Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas|

AR110362A1|2016-12-22|2019-03-20|Dow Global Technologies Llc|PROCESS FOR CONVERTING SYNTHESIS GAS IN OLEFINS USING A CROMOZINC OXIDE BIFUNCTIONAL CATALYST - SAPO-34|

AR111149A1|2017-02-06|2019-06-12|Dow Global Technologies Llc|PROCESSES TO IMPROVE THE ACTIVITY OF HYBRID CATALYSTS|

CN108970600B|2017-06-02|2021-01-19|中国科学院大连化学物理研究所|Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas|

JP2020529388A|2017-08-08|2020-10-08|ビーエーエスエフソシエタス・ヨーロピアＢａｓｆＳｅ|Composition containing a zeolite-based material having a CHA-type skeleton, an alkaline earth metal and a composite metal oxide|

AR113267A1|2017-10-10|2020-03-11|Dow Global Technologies Llc|PROCESSES TO IMPROVE EFFICIENCY IN HYDROCARBON PRODUCTION|

CN109704900B|2017-10-26|2021-11-30|中国石油化工股份有限公司|Method for preparing olefin by synthesis gas one-step method|

CN109704898A|2017-10-26|2019-05-03|中国石油化工股份有限公司|Synthesis gas prepares the utilization method of olefin by-product carbon dioxide|

BR112020007909A2|2017-10-30|2020-11-03|Dow Global Technologies Llc|hybrid catalyst for selective and stable olefin production|

CN109939667B|2018-01-26|2021-01-05|中国科学院大连化学物理研究所|Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas|

CN109939728B|2018-01-26|2020-08-14|中国科学院大连化学物理研究所|Supported catalyst and method for preparing low-carbon olefin by directly converting synthesis gas|

EP3758841A1|2018-02-27|2021-01-06|Dow Global Technologies LLC|Catalyst and method for converting carbon-containing stream to c2 to c5 paraffins using it|

US20220055968A1|2018-09-18|2022-02-24|Dow Global Technologies Llc|Process for preparing c2-c5 hydrocarbons using a hybrid catalyst|

CN109317192B|2018-09-30|2021-04-27|宁夏大学|CO 2Core-shell catalyst for preparing low-carbon olefin by hydrogenation coupling and preparation thereof|

WO2020210092A1|2019-04-10|2020-10-15|Exxonmobil Chemical Patents Inc.|Multicomponent catalysts for syngas conversion to light hydrocarbons|

CN110152725A|2019-06-25|2019-08-23|华东理工大学|A kind of method of composite catalyst and the direct producing light olefins of synthesis gas|

CN110201711B|2019-07-11|2021-09-28|中国华能集团有限公司|Catalyst for synthesizing low-carbon mixed alcohol by carbon dioxide hydrogenation and preparation method thereof|

CN110479363A|2019-08-29|2019-11-22|太原理工大学|A kind of preparation method and applications of high-performance ZnCr/SAPO-34 bifunctional catalyst|

WO2021133523A1|2019-12-23|2021-07-01|Dow Global Technologies Llc|Synthesis gas to hydrocarbon processes with neutral or negative carbon dioxide-selectivity|

CN112588315B|2020-12-21|2022-03-04|中国科学院山西煤炭化学研究所|Chromium-based metal oxide-molecular sieve catalyst and preparation method and application thereof|

CN113134386B|2021-04-25|2022-02-11|中国科学院山西煤炭化学研究所|Gallium-zirconium composite oxide-molecular sieve catalyst, and preparation method and application thereof|

法律状态:
2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2020-12-29| 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 08/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US201462023500P| true| 2014-07-11|2014-07-11|

US62/023,500|2014-07-11|

PCT/US2015/039522|WO2016007607A1|2014-07-11|2015-07-08|Conversion of carbon monoxide, carbon dioxide, or a combination thereof over hybrid catalyst|

[返回顶部]