CN110813309A - Catalyst for directly preparing low-carbon olefin from synthesis gas - Google Patents

Catalyst for directly preparing low-carbon olefin from synthesis gas Download PDF

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CN110813309A
CN110813309A CN201911019071.5A CN201911019071A CN110813309A CN 110813309 A CN110813309 A CN 110813309A CN 201911019071 A CN201911019071 A CN 201911019071A CN 110813309 A CN110813309 A CN 110813309A
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catalyst
low
carrier
carbon olefin
synthesis gas
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杜成荣
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for directly preparing low-carbon olefin from synthesis gas, which comprises active ingredients, an auxiliary agent and a spherical carrier, wherein the active ingredients are iron and cobalt, and account for 10-50% of the weight of the catalyst; the auxiliary agent is manganese, and accounts for 5 to up to 5 percent of the weight of the catalyst30 percent; the spherical carrier is selected from Al2O3、TiO2Or one or more of active carbon, wherein the weight of the spherical carrier accounts for 20-80% of the weight of the catalyst; the spherical carrier is a nonporous carrier with spherical or ellipsoidal shape of primary particles, and the size of the carrier particles is 100-1500 nm. The invention has the beneficial effects that: the preparation cost is low; the supported catalyst improves the heat transfer efficiency of the catalyst, and can effectively solve the problem that the catalyst is quickly deactivated because heat cannot be dissipated in time; the catalyst can also promote the generated low-carbon olefin to diffuse quickly on the surface of the catalyst, and avoid the secondary reaction of the low-carbon olefin and the catalyst, thereby effectively improving the selectivity of the low-carbon olefin.

Description

Catalyst for directly preparing low-carbon olefin from synthesis gas
Technical Field
The invention belongs to the technical field of low-carbon olefin preparation, and particularly relates to a catalyst for directly preparing low-carbon olefin from synthesis gas.
Background
The low-carbon olefin comprises ethylene, propylene and butylene, and is an important raw material for synthesizing plastics, fibers and various chemical materials. Currently, low carbon olefins are mainly produced by petrochemical routes of naphtha cracking.
China is rich in coal resources, and the coal is used as a raw material to obtain synthesis gas (namely CO and H) through gasification2The mixed gas) and then the synthesis gas is converted into methanol, and the process of preparing olefin (MTO) from methanol is mature and is already in industrialization. Compared with the indirect way of preparing olefin by methanol, the route of directly preparing olefin from the synthesis gas by one-step method has the characteristics of simple process and less equipment investment.
The direct preparation of low-carbon olefin from synthesis gas refers to synthesis gas (CO and H)2) A process for preparing olefins with a carbon number less than or equal to 4 by Fischer-Tropsch synthesis in the presence of a catalyst, by-production of water and CO2. The Fischer-Tropsch synthesis product distribution is limited by an Anderson-Schulz-Flory rule (the molar distribution of chain growth decreasing according to an index), and the strong exothermicity of the reaction is easy to cause the generation of methane and low-carbon alkane, and the generated olefin is promoted to carry out secondary reaction, so that the low-carbon olefin is difficult to obtain with high selectivity, and the key point is the development of a high-performance catalyst.
In order to improve the selectivity of directly preparing the low-carbon olefin from the synthesis gas, the Fischer-Tropsch synthesis catalyst can be physically and chemically modified, for example, the proper pore channel structure of a molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from a metal active center in time, and the secondary reaction of the low-carbon olefin is inhibited; the metal ion dispersibility is improved, and the olefin selectivity is better; the selectivity of the low-carbon olefin can also be improved by changing the interaction between the metal and the carrier; proper transition metal is added, so that the bond energy of the active component and carbon can be enhanced, the generation of methane is inhibited, and the selectivity of low-carbon olefin is improved; the electron promoting assistant is added to promote the increase of CO chemical adsorption heat, the increase of adsorption quantity and the decrease of hydrogen adsorption quantity, so that the selectivity of the low-carbon olefin is increased; eliminating the acid center of the catalyst can inhibit the secondary reaction of low carbon olefin and raise the selectivity.
The carrier with the spherical shape is adopted to load the active component Fe, so that the active component Fe can be effectively exposed on the spherical outer surface, and the electronic structure of the surface of the active phase is adjusted by adopting some metal or nonmetal auxiliary agents, thereby being beneficial to forming the iron carbide active phase with a unique structure and simultaneously reducing the probability of secondary reaction of the generated olefin on an active site. Especially when the catalyst loaded by the spherical carrier is applied to a fluidized bed or slurry bed reactor, the fine particles participate in the catalytic reaction of the synthesis gas, which is beneficial to solving the problems of reaction heat removal and rapid diffusion of olefin from the surface of the active phase of the catalyst to the main phase, thereby greatly improving the selectivity of the olefin.
Disclosure of Invention
The invention aims to provide a catalyst for directly preparing low-carbon olefin from synthesis gas, and solves the problem of low selectivity of the catalyst for directly preparing low-carbon olefin from synthesis gas in the prior art.
The technical scheme adopted by the invention is that the catalyst for directly preparing low-carbon olefin from synthesis gas comprises active ingredients, an auxiliary agent and a spherical carrier, wherein the active ingredients are iron and cobalt, and account for 10-50% of the weight of the catalyst; the auxiliary agent is manganese which accounts for 5 to 30 percent of the weight of the catalyst; the spherical carrier is selected from Al2O3、TiO2Or one or more of active carbon, wherein the weight of the spherical carrier accounts for 20-80% of the weight of the catalyst; the spherical carrier is a nonporous carrier with spherical or ellipsoidal shape of primary particles, and the particle size of the carrier is 100-1500 nm.
The invention is also characterized in that:
the iron element is Fe2O3、Fe3O4One or two of them.
The cobalt element is cobaltosic oxide.
The manganese element is one or more of manganese oxides.
The specific surface area of the spherical carrier is 300-900 m2·g-1。
The pore diameter distribution of the spherical carrier is less than or equal to 2nm, and the pores account for 65-95 percent.
The invention has the beneficial effects that: the catalyst for directly preparing the low-carbon olefin from the synthesis gas has low preparation cost; the load type catalyst can reduce the load of active ingredients, improve the heat transfer efficiency of the catalyst and effectively solve the problem that the catalyst is quickly deactivated because the heat of the catalyst cannot be dissipated in time; the catalyst can also promote the generated low-carbon olefin to diffuse quickly on the surface of the catalyst, and avoid the secondary reaction of the low-carbon olefin and the catalyst, thereby effectively improving the selectivity of the low-carbon olefin.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas, which comprises an active ingredient, an auxiliary agent and a spherical carrier, wherein the active ingredient is iron and cobalt which account for 10-50% of the weight of the catalyst, and the iron element is Fe2O3、Fe3O4One or two of them, cobalt element is cobaltosic oxide; the auxiliary agent is manganese which accounts for 5-30% of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical carrier is selected from Al2O3、TiO2Or one or more of active carbon, the weight of the spherical carrier accounts for 20-80% of the weight of the catalyst, the spherical carrier is a nonporous carrier with a primary particle having a spherical or ellipsoidal shape, the particle size of the carrier is 100-1500 nm, and the specific surface area of the spherical carrier is 300-900 m2·g-1The pore diameter distribution of pores with the diameter less than or equal to 2nm accounts for 65-95 percent.
The carrier with the spherical shape is adopted to load the active component Fe, so that the active component Fe can be effectively exposed on the spherical outer surface, the manganese auxiliary agent is added into the catalyst, the electronic structure of the surface of the active phase can be adjusted, the formation of the iron carbide active phase with a unique structure is facilitated, the probability of secondary reaction of the generated olefin on an active site can be reduced, the content of low-carbon olefin in the product is improved, the generation of methane is inhibited, and the selectivity of the olefin is enabled to be more than 50%.
Example 1
Preparing a catalyst for directly preparing low-carbon olefin by using synthesis gas, wherein the active component isIron and cobalt, the iron element being Fe2O36 percent of cobalt element, 4 percent of cobaltosic oxide, accounting for 10 percent of the weight of the catalyst; the auxiliary agent is manganese which accounts for 30 percent of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical carrier is selected from Al2O3The weight of the spherical carrier accounts for 80 percent of the weight of the catalyst, the spherical carrier is a nonporous carrier with a primary particle having a spherical or ellipsoidal shape, the size of the carrier particle is 1500nm, and the specific surface area of the spherical carrier is 300m2·g-1And the pores with the diameter less than or equal to 2nm account for 65 percent of the total pore diameter distribution.
The catalyst is used for synthesizing low-carbon olefin by catalyzing synthesis gas, and the technological parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1The CO conversion was found to be 25.2%, C2～C4The percentage was 39.8%.
Example 2
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas, wherein the active components of the catalyst are iron and cobalt which account for 35 percent of the weight of the catalyst, and the iron element is Fe3O425 percent of cobalt element, and 10 percent of cobaltosic oxide; the auxiliary agent is manganese which accounts for 25 percent of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical support is selected from TiO2The weight of the spherical carrier accounts for 40 percent of the weight of the catalyst, the spherical carrier is a nonporous carrier with primary particles having spherical or ellipsoidal morphology, the size of the carrier particles is 1200nm, and the specific surface area of the spherical carrier is 400m2·g-1And the pores with the diameter less than or equal to 2nm account for 75 percent of the total pore diameter distribution.
The catalyst is used for synthesizing low-carbon olefin by catalyzing synthesis gas, and the technological parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1The CO conversion was found to be 25.2%, C2～C4The percentage was 39.8%.
Example 3
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas, wherein the active components of the catalyst are iron and cobalt which account for 30 percent of the weight of the catalyst, and the iron element is Fe2O3、Fe3O410 percent of the cobalt element and 20 percent of cobaltosic oxide; the auxiliary agent is manganese which accounts for 20 percent of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical carrier is activated carbon, the weight of the spherical carrier accounts for 50 percent of the weight of the catalyst, the spherical carrier is a nonporous carrier with a primary particle having a spherical or ellipsoidal shape, the particle size of the carrier is 500nm, and the specific surface area of the spherical carrier is 600m2·g-1And the pore diameter distribution of pores with the diameter less than or equal to 2nm accounts for 80 percent.
The catalyst is used for synthesizing low-carbon olefin by catalyzing synthesis gas, and the technological parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1The CO conversion was found to be 30.1%, C2～C4The percentage was 44.5%.
Example 4
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas, wherein the active components of the catalyst are iron and cobalt which account for 40 percent of the weight of the catalyst, and the iron element is Fe2O3、Fe3O4The content is 15 percent, the cobalt element is cobaltosic oxide, and the content is 10 percent; the auxiliary agent is manganese which accounts for 15 percent of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical carrier is selected from Al2O3、TiO2The weight of the spherical carrier accounts for 60 percent of the weight of the catalyst, the spherical carrier is a nonporous carrier with a primary particle having a spherical or ellipsoidal shape, the size of the carrier particle is 800nm, and the specific surface area of the spherical carrier is 800m2·g-1And the pores with the diameter less than or equal to 2nm account for 90 percent of the total pore diameter distribution.
The catalyst is used for synthesizing low-carbon olefin by catalyzing synthesis gas, and the technological parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1The CO conversion rate is testedIs 32.6, C2～C4The percentage was 48.2%.
Example 5
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas, wherein the active components of the catalyst are iron and cobalt which account for 50 percent of the weight of the catalyst, and the iron element is Fe2O3、Fe3O415 percent and 30 percent respectively, and the cobalt element is cobaltosic oxide with the content of 5 percent; the auxiliary agent is manganese which accounts for 30 percent of the weight of the catalyst, and the manganese element is one or more of manganese oxides; the spherical support is selected from TiO2Or active carbon, the weight of the spherical carrier accounts for 20 percent of the weight of the catalyst, the spherical carrier is a nonporous carrier with primary particles having a spherical or ellipsoidal shape, the size of the carrier particles is 100nm, and the specific surface area of the spherical carrier is 900m2·g-1And the pore diameter distribution of pores with the diameter less than or equal to 2nm accounts for 95 percent.
The catalyst is used for synthesizing low-carbon olefin by catalyzing synthesis gas, and the technological parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1Test results show that the CO conversion is 35.8 percent, C2～C4The percentage was 50.1%.
From examples 1 to 5, it can be seen that the catalyst is used for catalytically synthesizing low-carbon olefins by using synthesis gas, and the process parameters of the synthesis gas are as follows: h2The ratio of CO to CO is 0.5-5, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-1 MPa, and the reaction space velocity is 500-5000 h-1And the tested CO conversion rate is 25.2-35.8 percent, and C2～C4The percentage is 39.8% -50.1%. Therefore, the supported iron-based catalyst can reduce the load capacity of iron, improve the heat transfer efficiency of the catalyst and effectively solve the problem that the catalyst is quickly deactivated because heat cannot be dissipated in time; the catalyst can also promote the generated low-carbon olefin to diffuse quickly on the surface of the catalyst, and avoid the secondary reaction of the low-carbon olefin and the catalyst, thereby effectively improving the selectivity of the low-carbon olefin.

Claims (6)

1. The catalyst for directly preparing the low-carbon olefin from the synthesis gas is characterized by comprising an active component, an auxiliary agent and a spherical carrier
Wherein, the active components are iron and cobalt, which account for 10-50% of the weight of the catalyst; the auxiliary agent is manganese which accounts for 5 to 30 percent of the weight of the catalyst;
the spherical carrier is selected from Al2O3、TiO2Or one or more of active carbon, wherein the weight of the spherical carrier accounts for 20-80% of the weight of the catalyst.
The spherical carrier is a nonporous carrier with spherical or ellipsoidal shape of primary particles, and the size of the carrier particles is 100-1500 nm.
2. The catalyst for directly preparing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein the iron element is Fe2O3、Fe3O4One or two of them.
3. The catalyst for directly preparing the low-carbon olefin by the synthesis gas as claimed in claim 1, wherein the cobalt element is cobaltosic oxide.
4. The catalyst for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the manganese element is one or more of oxides of manganese.
5. The catalyst for directly preparing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein the specific surface area of the spherical carrier is 300-900 m2·g-1。
6. The catalyst for directly preparing the low-carbon olefin by the synthesis gas as claimed in claim 1, wherein the pore size distribution of the spherical carrier is 65-95% of pores with the diameter of less than or equal to 2 nm.
CN201911019071.5A 2019-10-24 2019-10-24 Catalyst for directly preparing low-carbon olefin from synthesis gas Pending CN110813309A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2301500A1 (en) * 1975-02-19 1976-09-17 Kolbel Herbert Hydrocarbons from gases contg carbon monoxide and hydrogen - by contact with a catalyst contg manganese and opt iron
EP1268056A1 (en) * 2000-04-07 2003-01-02 Shell Internationale Researchmaatschappij B.V. A process for producing hydrocarbons, and a catalyst suitable for use in the process
EP2422876A1 (en) * 2010-08-20 2012-02-29 Shell Internationale Research Maatschappij B.V. Process for preparing olefins from synthesis gas using a cobalt and manganese containing catalyst
US20120259026A1 (en) * 2009-10-23 2012-10-11 Hirsa Maria Torres Galvis Production of lower olefins from synthesis gas
CN103521240A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing olefin employing synthesis gas and preparation method thereof
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst
CN105363464A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2301500A1 (en) * 1975-02-19 1976-09-17 Kolbel Herbert Hydrocarbons from gases contg carbon monoxide and hydrogen - by contact with a catalyst contg manganese and opt iron
EP1268056A1 (en) * 2000-04-07 2003-01-02 Shell Internationale Researchmaatschappij B.V. A process for producing hydrocarbons, and a catalyst suitable for use in the process
US20120259026A1 (en) * 2009-10-23 2012-10-11 Hirsa Maria Torres Galvis Production of lower olefins from synthesis gas
EP2422876A1 (en) * 2010-08-20 2012-02-29 Shell Internationale Research Maatschappij B.V. Process for preparing olefins from synthesis gas using a cobalt and manganese containing catalyst
CN103521240A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing olefin employing synthesis gas and preparation method thereof
CN105363464A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SERGIO L ET.AL: "SYNTHESIS OF LIGHT ALKENES ON MANGANESE PROMOTED IRON AND IRON-COBALT FISCHER-TROPSCH CATALYSTS", 《REACTION KINETICS AND CATALYSIS LETTERS》 *

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Application publication date: 20200221