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WO2017130081A1 - Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2 - Google Patents

Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2 Download PDF

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Publication number
WO2017130081A1
WO2017130081A1 PCT/IB2017/050262 IB2017050262W WO2017130081A1 WO 2017130081 A1 WO2017130081 A1 WO 2017130081A1 IB 2017050262 W IB2017050262 W IB 2017050262W WO 2017130081 A1 WO2017130081 A1 WO 2017130081A1
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Prior art keywords
reactor
section
catalyst
temperature
light olefins
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Inventor
Venkatesan CHITHRAVEL
Rajitha VUPPULA
Bharmana MALVI
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry

Definitions

  • the presently disclosed subject matter relates to processes and systems for increasing selectivity for light olefins in C0 2 hydrogenation.
  • Light olefins e.g., C 2 -C 4 olefins
  • Light olefins such as ethylene, propylene, and butene isomers (1-butene, czs-2-butene, trans-2-butene, and isobutylene) are widely used as feedstocks for polymerization, among many other uses.
  • C0 2 carbon dioxide
  • Light olefins can be prepared from C0 2 by reaction of C0 2 with hydrogen (H 2 ). This process can be described as a hydrogenation of C0 2 .
  • C0 2 and H 2 can be converted to light olefins through a two-step process. First, C0 2 and H 2 can be converted to carbon monoxide (CO) and water (H 2 0) through a reverse water gas shift (RWGS) reaction.
  • the RWGS reaction is endothermic and can be described by Equation 1 :
  • Equation 3 it may also be possible under certain conditions to convert C0 2 and H 2 directly to hydrocarbons through the exothermic reaction presented in Equation 3 :
  • CH 2 represents a generic hydrocarbon moiety that can be incorporated into a larger molecule, e.g., ethylene (C 2 H 4 ).
  • Process conditions can alter the product distribution of the FT reaction. For example, increased space velocity can increase selectivity for light olefins, while increased temperature can reduce selectivity for light olefins. See, e.g., M. Hirsa, T. Galvis and K. P. de Jong, ACS Catal. 2013, 3, 2130-2149.
  • selectivity for light olefins and the overall product distribution of a FT reaction can generally be governed by the Anderson- Schulz-Flory (ASF) model. Under the ASF model, C 2 -C 4 content of the product mixture in an FT reaction can range up to about 56% maximum. See, e.g., M. Hirsa, T. Galvis and K. P. de Jong, ACS Catal. 2013, 3, 2130-2149.
  • ASF Anderson- Schulz-Flory
  • 1,045,283 to Xu et al. describe direct conversion of C0 2 and H 2 to light olefins within a single reactor.
  • the RWGS reaction is endothermic and consequently can require a high reaction temperature
  • the FT reaction is highly exothermic and consequently can require a lower reaction temperature.
  • conducting the FT reaction at high temperature can reduce selectivity for C 2 -C 4 olefins and can induce undesirable olefin hydrogenation (to form alkane products).
  • an exemplary process for conversion of C0 2 and H 2 into light olefins can include providing a reactor that includes at least a first section and a second section.
  • the temperature of the first section of the reactor can be higher than the temperature of the second section of the reactor.
  • the reactor can include a catalyst.
  • the process can further include passing a reaction mixture that includes C0 2 and H 2 through the first section of the reactor, to provide a mixture that includes CO, H 2 0, and H 2 .
  • the process can additionally include passing the mixture that includes CO, H 2 0, and H 2 through the second section of the reactor, to provide a product mixture that includes light olefins.
  • the reactor can be axially oriented.
  • the temperatures of the first and second sections of the reactor can be between about 250 °C and about 500 °C.
  • the temperature of the first section of the reactor can be about 400 °C and the temperature of the second section of the reactor can be less than or equal to about 350 °C.
  • the second section of the reactor can include a temperature gradient.
  • the temperature gradient can span a temperature range of about 350 °C to about 325 °C.
  • the temperature gradient can vary by about 4 °C per cm.
  • the reactor can include a catalyst bed.
  • a first portion of the catalyst bed can be located in the first section of the reactor and a second portion of the catalyst bed can be located in the second section of the reactor.
  • the catalyst bed can be axially oriented.
  • the catalyst can be solid-supported.
  • the catalyst can be supported on alumina.
  • the catalyst can include iron (Fe).
  • the catalyst can include potassium (K).
  • the catalyst can include both iron (Fe) and potassium (K).
  • the reaction mixture of C0 2 and H 2 can include C0 2 and H 2 in a molar ratio of about 1 :3.
  • the product mixture can include one or more C 2 -C 4 olefins selected from the group consisting of ethylene, propylene, 1-butene, czs-2-butene, trans-2-butene, and isobutylene.
  • the product mixture can include at least 30 mol% C 2 -C 4 olefins, on carbon basis.
  • an exemplary system for conversion of C0 2 and H 2 into light olefins can include an axially oriented reactor that includes at least a first section and a second section. The temperature of the first section of the reactor can be higher than the temperature of the second section of the reactor.
  • a catalyst bed can be positioned within the reactor. A first portion of the catalyst bed can be located in the first section of the reactor, and a second portion of the catalyst bed can be located in the second section of the reactor.
  • the catalyst bed can include a catalyst capable of catalyzing both a reverse water gas shift reaction of C0 2 and H 2 to CO and H 2 0 and a Fischer-Tropsch reaction of CO and H 2 to light olefins.
  • the system can additionally include a reaction mixture feed line adapted to feed a reaction mixture that includes C0 2 and H 2 into the reactor.
  • the system can further include a product mixture line adapted to remove a product mixture that includes light olefins from the reactor.
  • FIG. 1 is a schematic diagram showing an exemplary system for conversion of C0 2 and H 2 into light olefins, in accordance with non-limiting embodiments of the disclosed subject matter.
  • FIG. 2 is a schematic diagram comparing an exemplary system for conversion of C0 2 and H 2 into light olefins, in accordance with non-limiting embodiments of the disclosed subject matter ("Non-isothermal conditions," FIG. 2B) with an exemplary isothermal system ("Isothermal conditions,” FIG. 2A).
  • FIG. 3 includes a schematic diagram showing an exemplary system for conversion of C0 2 and H 2 into light olefins, in accordance with non-limiting embodiments of the disclosed subject matter (FIG. 3 A).
  • FIG. 3 also includes a schematic diagram showing catalyst position within the exemplary system (FIG. 3B).
  • FIG. 3 further includes a plot presenting temperature within the exemplary system, as compared to temperature within an isothermal system (FIG. 3C).
  • the presently disclosed subject matter provides processes and systems for preparation of light olefins from C0 2 and H 2 with improved conversion, yield, selectivity, and energy efficiency.
  • the presently disclosed processes and systems can include use of a single reactor for direct conversion of C0 2 and H 2 and can take advantage of temperature gradient across the reactor, which can allow the reverse water gas shift (RWGS) and Fischer-Tropsch (FT) reactions to occur at different temperatures.
  • RWGS reverse water gas shift
  • FT Fischer-Tropsch
  • the term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean a range of up to 20%, up to 10%, up to 5%), and or up to 1% of a given value.
  • Catalysts suitable for use in conjunction with the presently disclosed subject matter can be catalysts capable of catalyzing both RWGS and FT reactions.
  • the catalyst can be a bifunctional or dual-function catalyst.
  • the catalyst can be located in a packed bed, i.e., a catalyst bed.
  • the catalyst can include one or more transition metals.
  • the transition metal can include iron (Fe), cobalt (Co), manganese (Mn), copper (Cu), zinc (Zn), or a mixture thereof.
  • the catalyst can include an alkali metal, e.g., lithium (Li), sodium (Na), potassium (K), cesium (Cs), or a mixture thereof.
  • the catalyst can include an alkaline earth metal, e.g., magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or a mixture thereof.
  • the catalyst can include a solid support. That is, the catalyst can be solid-supported.
  • the solid support can include various metal salts, metalloid oxides, and metal oxides, e.g., titania (titanium oxide), zirconia (zirconium oxide), silica (silicon oxide), alumina (aluminum oxide), magnesia (magnesium oxide), and magnesium chloride.
  • the solid support can include alumina (A1 2 0 3 ), silica (Si0 2 ), magnesia (MgO), titania (Ti0 2 ), zirconia (Zr0 2 ), cerium(IV) oxide (Ce0 2 ), or a combination thereof.
  • the solid support can include a zeolite, e.g., silicalite-1, silicalite-2, mordenite, KL, ZSM-5, beta, HY, or a combination thereof.
  • the catalyst can be a catalyst that includes iron and potassium ⁇ i.e., a Fe-K catalyst) supported on alumina.
  • the catalyst includes one or more transition metals and one or more alkali metals on a solid support, the transition metal(s) and alkali metal(s) can be present in a combined amount of approximately 1% to about 50%, by weight, as compared to the total weight of the catalyst.
  • the combined weight of metal can be about 25% of the total weight, e.g., 24%.
  • Fe can constitute about 14% of the total weight of the catalyst and K can constitute about 10% of the total weight of the catalyst, with the remainder being alumina.
  • FIGS. 1 and 2B present schematic representations of exemplary systems according to the disclosed subject matter.
  • the exemplary system 100, 200 can be used to convert C0 2 and H 2 into light olefins.
  • the system 100, 200 can include an axially oriented reactor 102, 202, i.e., a reactor laid out along a straight line.
  • the reactor 102, 202 can be a fixed bed reactor or a moving bed reactor.
  • the axially oriented reactor 102, 202 can be vertically oriented such that reactants are added at the top and products are removed from the bottom, with a flow of material from top to bottom.
  • the reactor 102, 202 can have a height greater than its width and can be mounted vertically.
  • the height to width ratio of the reactor 102, 202 which can also be expressed as a length to diameter ratio, can be equal to or greater than about 10: 1, e.g., about 10: 1, about 12: 1, about 15: 1, about 18: 1, about 20: 1, about 22: 1, about 25: 1, about 30: 1, about 35: 1, about 40: 1, about 45: 1, about 50: 1, about 55: 1, about 60: 1, about 65: 1, about 70: 1, about 80: 1, about 90: 1, about 100 : 1 , or greater than about 100: 1.
  • a laboratory scale reactor with a length of 40 cm can have an internal diameter (ID) of about 1 cm.
  • the reactor 102, 202 can be tubular, cylindrical, or rectangular. In certain embodiments, the reactor 102, 202 can be tubular or cylindrical.
  • the reactor 102, 202 can include a heating jacket and/or a heating mantle.
  • the reactor 102, 202 can include a first section 104, 204 and a second section 106, 206. As shown in FIG. 1, in certain embodiments, the first section 104, 204 can be positioned above the second section 106, 206. The temperature of the first section 104, 204 can be higher than the temperature of the second section 106, 206.
  • a catalyst bed 107, 207 can be positioned within the reactor 102, 202 and can be axially oriented along the same axis as the reactor 102, 202. As shown in FIG. 1, a first portion 108 of the catalyst bed can be located in the first section of the reactor 104, and a second portion 109 of the catalyst bed can be located in the second section of the reactor 106.
  • the catalyst bed 107, 207 can include a catalyst capable of catalyzing both a reverse water gas shift (RWGS) reaction of C0 2 and H 2 to CO and H 2 0 and a Fischer-Tropsch (FT) reaction of CO and H 2 to light olefins.
  • the system 100, 200 can additionally include a reaction mixture feed line 1 10, 210 adapted to feed a reaction mixture that includes C0 2 and H 2 into the reactor 102, 202.
  • the system can further include a product mixture line 1 12, 212 adapted to remove a product mixture that includes light olefins from the reactor 102, 202.
  • the catalyst bed 107, 207 can occupy a portion of the reactor 102, 202 such that there are inert regions of the reactor 102, 202 above and below the catalyst bed 107, 207.
  • the inert regions of the reactor can be packed with an inert material.
  • the inert material can be an inert material known in the art and can include one or more ceramics, glasses (e.g., glass beads), metal oxides (e.g., aluminum oxide), carbides (e.g., silicon carbide), and metals.
  • an exemplary laboratory scale reactor can be vertically oriented and can have a height of 40 cm.
  • the catalyst bed can have a height of 18 cm and can occupy a central portion of the reactor. Inert regions of the reactor, each having a height of 1 1 cm, can be positioned above and below the catalyst bed.
  • the temperature of the first section 104, 204 of the reactor 102, 202 can be higher than the temperature of the second section 106, 206 of the reactor.
  • the temperatures of the first section 104, 204 and second section 106, 206 can be between about 250 °C and about 500 °C.
  • the temperature in the first section 104, 204 can be between about 300 °C and about 500 °C, e.g., about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C, about 400 °C, about 410 °C, about 420 °C, about 430 °C, about 440 °C, about 450 °C, about 460 °C, about 470 °C, about 480 °C, about 490 °C, or about 500 °C.
  • the temperature in the first section 104, 204 can be adjusted to improve the yield and selectivity of a RWGS reaction.
  • the temperature in the second section 106, 206 can be between about 250 °C and about 400 °C, e.g., about 250 °C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C, or about 400 °C.
  • the temperature in the second section 106, 206 can be adjusted to improve the yield and selectivity of a FT reaction.
  • FIG. 2 compares a system in accordance with the presently disclosed subject matter (FIG. 2B) with an isothermal system (FIG. 2A).
  • FIG. 2B compares a system in accordance with the presently disclosed subject matter
  • FIG. 2A isothermal system
  • the temperature is constant throughout the reactor.
  • a temperature gradient can be established along a portion of the axis of the reactor 102, 202 such that the temperature gradually changes within one or both of the first section 104, 204 and the second section 106, 206.
  • a temperature gradient can be established within the second section of the reactor 106, 206.
  • the area of the second section nearest to the boundary between the second section of the reactor and the first section can be heated to a relatively high temperature, and the temperature can gradually be reduced at increasing distance from the boundary.
  • the temperature gradient within the second section of the reactor 106, 206 can span a range of temperature from about 400 °C to about 250 °C, e.g., about 400 °C to about 350 °C, about 400 °C to about 375 °C, about 375 °C to about 350 °C, about 375 °C to about 325 °C, about 350 °C to about 325 °C, about 350 °C to about 300 °C, about 325 °C to about 300 °C, about 325 °C to about 275 °C, about 300 °C to about 275 °C, about 300 °C to about 250 °C, or about 275 °C to about 250 °C.
  • FIG. 3 An exemplary temperature gradient is shown in FIG. 3.
  • a vertically oriented reactor containing a catalyst bed is shown in FIG. 3A.
  • the catalyst bed has a length of 18 cm.
  • the temperature within the catalyst bed gradually decreases from Ti (400 °C) to T 3 (325 °C).
  • the temperature gradient varies by 4.167 °C per cm, or about 4 °C per cm.
  • An exemplary process for conversion of C0 2 and H 2 into light olefins can include use of an exemplary system 100, 200 that includes a reactor 102, 202 divided into a first section 104, 204 and a second section 106, 206.
  • the process can include feeding a reaction mixture that includes C0 2 and H 2 into the reactor 102, 202 through a reaction mixture feed line 110, 210.
  • the ratio of C0 2 and H 2 in the reaction mixture can be varied as is known in the art.
  • the molar ratio of C0 2 and H 2 can be in a range from about 1 :2 to about 1 :5, e.g., about 1 :3.
  • the reaction mixture can also include components other than C0 2 andH 2 , e.g., CO.
  • the reaction mixture can include CO and can include CO, C0 2 , and H 2 in a ratio between about 0.05: 1 :2 and about 1 : 1 :5.
  • the reaction mixture can be passed through the first section of the reactor 104, 204 and undergo a RWGS reaction, to provide a mixture that includes CO, H 2 0, and unreacted H 2 .
  • the mixture that includes CO, H 2 0, and H 2 can then be passed through the second section of the reactor 106, 206 to undergo a FT reaction and provide a product mixture that includes light olefins.
  • the temperature of the first section 104, 204 can be higher than the temperature of the second section 106, 206.
  • the temperature of the first section 104, 204 can be adjusted to a improve the conversion, yield, and selectivity of the RWGS reaction, while the temperature of the second section 106, 206 can be adjusted separately to improve the conversion, yield, and selectivity of the FT reaction.
  • the product mixture can be removed from the reactor 102, 202 through the product mixture line 112, 212.
  • the product mixture can include one or more C2-C4 olefins.
  • the one or more C2-C4 olefins can include ethylene, propylene, 1-butene, czs-2-butene, trans-2-butene, and/or isobutylene.
  • the product mixture can include at least 20 mol% C2-C4 olefins, as measured on carbon basis (i.e., measured per mole of C0 2 consumed), e.g., about 20 mol%, about 22 mol%, about 25 mol%, about 30 mol%, about 35 mol%, about 40 mol%, about 45 mol%, about 50 mol%, or more than about 50 mol% C2-C4 olefins on carbon basis.
  • the product mixture can also include CO2, CO, methane (CH 4 ) and other paraffins, and/or heavier olefins (e.g., C 5 , C 6 , C 7 , C 8 , and/or higher olefins).
  • Components of the product mixture can be separated via techniques known in the art, e.g., cryogenic distillation.
  • the processes and systems of the presently disclosed subject matter can have advantages over other techniques for extraction and purification of butadiene.
  • operation of the second section of the reactor 106, 206 at a lower temperature than the first section of the reactor 104, 204 can reduce the required energy input, which can help to reduce overall energy consumption.
  • the presently disclosed subject matter also enables preparation of C2-C4 olefins with improved selectivity and yield and fewer side products (e.g., CO and methane) as compared to techniques that use an isothermal reactor.
  • selectivity for C2-C4 olefins, on carbon basis can be about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%), or about 50% higher in the processes and systems of the presently disclosed subject matter as compared to isothermal processes and systems.
  • An isothermal reactor in accordance with FIG. 2 A and a non-isothermal reactor in accordance with FIG. 2B were provided.
  • the isothermal reactor had an internal temperature of 400 °C.
  • the non-isothermal reactor included a temperature gradient, as shown in FIG. 2B, such that the temperature of the first section of the reactor was about 400 °C while the temperature of the second section of the reactor varied from about 350 °C to about 325 °C.
  • Both reactors had a catalyst bed length of 18 cm, an internal diameter of 1 cm, and a catalyst bed volume of approximately 14 cc.
  • Both reactors included an Fe-K catalyst supported on AI2O3, wherein 14% of the weight of the catalyst was Fe, 10% of the weight of the catalyst was K, and the remainder was alumina.
  • a reaction mixture that included C0 2 and H 2 in a molar ratio of 1 :3 was fed into the top of each reactor.
  • the gas hourly space velocity (GHSV) of the reactors was 1500 h "1 .
  • the pressure of the reactors was 2.1 MPa.
  • a product mixture was removed from the bottom of each rector. The composition of the product mixture was then analyzed by GC.
  • C 2 -C4 products include both alkanes and alkenes and include ethane, ethylene, propane, propylene, n-butane, 1-butene, czs-2-butene, tram--2-butene, and isobutylene.
  • Heavies include C 5 and C 6 olefins
  • "o/p for C 2 -C 4 products” is the olefin to paraffin ratio for the C 2 -C4 products, i.e., the ratio of C 2 -C 4 olefins to C 2 -C 4 alkanes. Table 1.
  • Non-isothermal reactor Use of a non-isothermal reactor provided a process for conversion of C0 2 and H 2 into light olefins with greater than 30 mol%> selectivity for C2-C4 olefins, on carbon basis. Selectivity for C2-C4 olefins was approximately 36% higher in the non-isothermal reactor than in the isothermal reactor.
  • Example 1 shows that the non-isothermal reactors of the presently disclosed subject matter can provide C2-C4 olefins from C0 2 and H 2 with improved selectivity, improved yield, and reduced side product formation as compared to isothermal systems.

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Abstract

La présente invention concerne des procédés de conversion de CO2 et H2 en oléfines légères. Un procédé exemplaire peut comprendre le passage de CO2 et H2 à travers un réacteur qui comprend un gradient de température, de sorte qu'une réaction de déplacement eau-gaz inverse se produise à une température relativement élevée et une réaction de Fischer-Tropsch se produit ensuite à une température relativement basse. L'invention concerne en outre des systèmes de conversion de CO2 et H2 en oléfines légères.
PCT/IB2017/050262 2016-01-27 2017-01-18 Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2 Ceased WO2017130081A1 (fr)

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KR20190136978A (ko) 2018-05-30 2019-12-10 한국화학연구원 에너지 효율적인 이산화탄소의 전환 시스템 및 방법
CN110871075A (zh) * 2018-08-30 2020-03-10 南京理工大学 负载铁钴钾的二氧化锆催化剂、制备方法及其应用
WO2021178369A1 (fr) * 2020-03-02 2021-09-10 Saudi Arabian Oil Company Boue rouge activée par du potassium utilisée comme catalyseur pour former des hydrocarbures à partir de dioxyde de carbone
CN113694724A (zh) * 2021-08-26 2021-11-26 无锡碳谷科技有限公司 一种用于捕获及催化co2的反应系统
CN114173922A (zh) * 2019-04-02 2022-03-11 牛津大学创新有限公司 基于铁-锰的催化剂、催化剂前体和催化方法
JP2022102704A (ja) * 2020-12-25 2022-07-07 Ｅｎｅｏｓ株式会社 反応装置
KR20230052455A (ko) 2021-10-13 2023-04-20 한국화학연구원 이산화탄소 함유 합성가스의 직접 전환 반응기 및 이를 이용한 선형 알파 올레핀의 제조방법
WO2024000353A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Procédés fischer-tropsch intégrés utilisant des catalyseurs de conversion inverse eau-gaz au manganèse
WO2024000370A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau
WO2024000397A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Procédés fischer-tropsch intégrés utilisant des catalyseurs de conversion inverse eau-gaz au nickel
WO2024000403A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Procédés fischer-tropsch intégrés utilisant du palladium et des catalyseurs de conversion eau-gaz inverse de platine
WO2024000381A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C Procédés fischer-tropsch intégrés utilisant des catalyseurs de conversion inverse eau-gaz à l'or
US12018392B2 (en) 2022-01-03 2024-06-25 Saudi Arabian Oil Company Methods for producing syngas from H2S and CO2 in an electrochemical cell

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CN112105593A (zh) * 2018-05-30 2020-12-18 韩国化学研究院 高能量效率的二氧化碳转换系统及方法
CN112105593B (zh) * 2018-05-30 2023-11-10 韩国化学研究院 高能量效率的二氧化碳转换系统及方法
US12116284B2 (en) 2018-05-30 2024-10-15 Korea Research Institute Of Chemical Technology Energy-efficient system and method for carbon dioxide conversion
CN110871075B (zh) * 2018-08-30 2022-03-22 南京理工大学 负载铁钴钾的二氧化锆催化剂、制备方法及其应用
CN110871075A (zh) * 2018-08-30 2020-03-10 南京理工大学 负载铁钴钾的二氧化锆催化剂、制备方法及其应用
CN109675573A (zh) * 2018-12-29 2019-04-26 华东理工大学 二氧化碳加氢制取高碳α-烯烃的催化剂和制备方法及应用
CN114173922A (zh) * 2019-04-02 2022-03-11 牛津大学创新有限公司 基于铁-锰的催化剂、催化剂前体和催化方法
CN114173922B (zh) * 2019-04-02 2025-06-17 牛津大学创新有限公司 基于铁-锰的催化剂、催化剂前体和催化方法
US11426708B2 (en) 2020-03-02 2022-08-30 King Abdullah University Of Science And Technology Potassium-promoted red mud as a catalyst for forming hydrocarbons from carbon dioxide
WO2021178369A1 (fr) * 2020-03-02 2021-09-10 Saudi Arabian Oil Company Boue rouge activée par du potassium utilisée comme catalyseur pour former des hydrocarbures à partir de dioxyde de carbone
JP2022102704A (ja) * 2020-12-25 2022-07-07 Ｅｎｅｏｓ株式会社 反応装置
JP7731195B2 (ja) 2020-12-25 2025-08-29 Ｅｎｅｏｓ株式会社 反応装置
CN113694724B (zh) * 2021-08-26 2023-01-10 无锡碳谷科技有限公司 一种用于捕获及催化co2的反应系统
CN113694724A (zh) * 2021-08-26 2021-11-26 无锡碳谷科技有限公司 一种用于捕获及催化co2的反应系统
KR20230052455A (ko) 2021-10-13 2023-04-20 한국화학연구원 이산화탄소 함유 합성가스의 직접 전환 반응기 및 이를 이용한 선형 알파 올레핀의 제조방법
US12018392B2 (en) 2022-01-03 2024-06-25 Saudi Arabian Oil Company Methods for producing syngas from H2S and CO2 in an electrochemical cell
WO2024000370A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau
WO2024000397A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Procédés fischer-tropsch intégrés utilisant des catalyseurs de conversion inverse eau-gaz au nickel
WO2024000403A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Procédés fischer-tropsch intégrés utilisant du palladium et des catalyseurs de conversion eau-gaz inverse de platine
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