CN109745965B - Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation - Google Patents
Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation Download PDFInfo
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Abstract
The invention belongs to a method for directly preparing low-carbon olefin by carbon monoxide hydrogenation, and particularly relates to a catalyst containing CeZr oxide and a method for directly converting carbon monoxide hydrogenation into low-carbon olefin, wherein synthesis gas is used as a reaction raw material, and a conversion reaction is carried out on a fixed bed or a moving bed, the catalyst adopted by the method is formed by compounding a component A and a component B, the component A is a composite metal oxide CexZr (1-x) O2, the component B is a molecular sieve, and the metal oxide and the molecular sieve are physically mixed to play a role in catalysis. The weight ratio of the component A to the component B is 0.1-20, the reaction process has high product yield and selectivity, particularly good stability, the selectivity of the low-carbon olefin after 650 hours of reaction can still be maintained to be 65-73%, the selectivity of the by-product methane is extremely low (< 15%), and the application prospect is good.
Description
Technical Field
The invention belongs to preparation of low-carbon olefin by carbon monoxide hydrogenation, and particularly relates to a catalyst and a method for preparing low-carbon olefin by directly converting carbon monoxide hydrogenation.
Background
The lower olefin is an olefin having 4 or less carbon atoms. The low-carbon olefin represented by ethylene and propylene is a very important basic organic chemical raw material, and the market of the low-carbon olefin is short in supply and demand for a long time along with the rapid growth of the economy of China. At present, the production of low-carbon olefin mainly adopts a petrochemical route of light hydrocarbon (ethane, naphtha and light diesel oil) cracking, and due to the gradual shortage of global petroleum resources and the long-term high-order running of the price of crude oil, the development of the tubular cracking furnace process which only depends on the light hydrocarbon as the raw material in the low-carbon olefin industry encounters larger and larger raw material problems, and the production process and the raw material of the low-carbon olefin need to be diversified. The process for preparing olefin by selecting synthesis gas can broaden the source of raw materials, and provides an alternative scheme for the steam cracking technology based on high-cost raw materials such as naphtha by using crude oil, natural gas, coal and renewable materials as raw materials to produce synthesis gas. The one-step method for directly preparing the low-carbon olefin from the synthesis gas is a process for directly preparing the low-carbon olefin with the carbon atom number less than or equal to 4 by the Fischer-Tropsch synthesis reaction of carbon monoxide and hydrogen under the action of the catalyst, and the process does not need to further prepare the olefin from the synthesis gas through methanol or dimethyl ether like an indirect process, thereby simplifying the process flow and greatly reducing the investment.
The direct preparation of low-carbon olefin from synthesis gas through Fischer-Tropsch synthesis becomes one of the research hotspots for developing Fischer-Tropsch synthesis catalysts. In patent CN1083415A published by institute of chemical and physical sciences in the chinese academy of sciences, an iron-manganese catalyst system supported by an alkali metal oxide of group IIA such as MgO or a high-silicon zeolite molecular sieve (or a phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, so that high activity (90% of CO conversion) and high selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction temperature of 300-400 ℃ under a reaction pressure of 1.0-5.0 MPa for preparing low-carbon olefin from synthesis gas. In patent ZL031095852 filed by Beijing university of chemical industry, a vacuum impregnation method is adopted to prepare a Fe/C catalyst taking manganese, copper, zinc, silicon, potassium and the like as auxiliaries, the Fe/C catalyst is used for reaction of preparing low-carbon olefin from synthesis gas, under the condition of no circulation of raw material gas, the conversion rate of CO is 96%, and the selectivity of the low-carbon olefin in hydrocarbon is 68%. Recently, a Netherlands university of Utrecht de Jong teaches a team that Fe supported by inert carriers such as SiC, carbon nanofibers and the like and Fe catalysts modified by auxiliaries such as Na, S and the like are adopted to achieve good progress and obtain 61% of low-carbon olefin selectivity, but when the conversion rate is increased, the selectivity is reduced. The reported catalyst adopts metallic iron or iron carbide as an active component, the reaction follows a chain growth reaction mechanism on the surface of metal, the selectivity of the product low-carbon olefin is low, particularly the selectivity of a single product such as ethylene is lower than 30%, and simultaneously, the methane content is higher than 15%.
Alumina-loaded ZnCr has recently been reported by the institute of encyclopedia of chemico-physical research, institute of academy and Panelea, China academy of sciences2O4The spinel oxide and the hierarchical pore SAPO-34 molecular sieve composite bifunctional catalyst realizes the selectivity of 80% of low-carbon olefin when the CO conversion rate is 17%, wherein the selectivity of the low-carbon alkane is 14, and the ratio of the olefin to the alkane (the alkene-alkane ratio) reaches 5.7. However, the stability of the catalyst still has a room for improvement, and particularly, the selectivity of the low-carbon olefin is obviously reduced by about 60 percent after 760h reaction.
Disclosure of Invention
Aiming at the problems, the invention provides a catalyst containing CeZr oxide and a method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation, particularly the catalyst has good stability, can maintain the selectivity of the low-carbon olefin after 650 hours of reaction and can still maintain the selectivity of the low-carbon olefin in the product to be 65-73%, and the methane selectivity is lower than 15%.
The technical scheme of the invention is as follows:
the catalyst containing the CeZr oxide is prepared by physically mixing a component A and a component B, wherein the active component of the component A is a composite metal oxide, the composite metal oxide is CexZr (1-x) O2, the component B is a molecular sieve, and the value of x is in the range of 0.6-0.98, preferably 0.8-0.98. Samples within the preferred range still exhibit better olefin selectivity and lower methane selectivity over a long reaction time.
The morphology of the composite metal oxide observed under a scanning electron microscope is rod-like or spherical, preferably rod-like. The rod-shaped sample exposes more active crystal faces compared with the spherical sample, and the surface Ce on the lower surface of the reaction atmosphere is better regulated4+/Ce3+The ratio of ions, and thus the surface oxygen vacancies can be modulated to make the olefin more favorableThe production of methane is suppressed.
The component B of the catalyst is a molecular sieve with CHA and AEI topological structures, and 8 circular ring pore canals and a proper cage size of the molecular sieve are favorable for generating low-carbon olefin.
The weight ratio of the active component in the catalyst A component to the B component is in the range of 0.1-20, preferably 0.3-5.
The composite metal oxide is composed of crystal grains with the size of 5-30nm, and a large number of oxygen holes exist in the distance range of 0.3nm from the surface of the crystal grains to the depth of the inner direction of the crystal grains, namely the molar quantity of oxygen atoms is less than 60% of the theoretical stoichiometric ratio, preferably the molar quantity of oxygen atoms is 60% -10% of the theoretical stoichiometric ratio, and more preferably 40-10%; surface oxygen vacancies are defined as (the molar amount of oxygen atoms is in the theoretical stoichiometric molar ratio content) and correspond to a molar ratio of oxygen vacancies of preferably 40 to 90%, more preferably 60 to 90%.
A dispersing agent can be optionally added into the component A, and the dispersing agent is Al2O3、SiO2、Cr2O3、ZrO2、TiO2And one or two of ZnO and composite metal oxide are dispersed in the dispersing agent, the content of the dispersing agent in the component A is 0.05-90 wt.%, and the balance is active composite metal oxide, and a proper amount of the dispersing agent is favorable for controlling the size of oxide nanoparticles and is favorable for catalyst molding.
The framework elements of the molecular sieve with the CHA and AEI topological structures can be one or more than two of Si-Al-O, Ga-Al-O, Ti-Si-O, Si-Al-P-O, Al-P-O, Ge-Al-O;
the physical mixing can be one or more of mechanical stirring, ball milling, table mixing and mechanical grinding.
A process for preparing low-carbon olefin by direct conversion of synthetic gas features that the synthetic gas is used as raw gas, and the said catalyst is used to perform conversion reaction on fixed or moving bed.
The synthesis gas is H2Mixed gas of/CO, H2The molar ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5; the pressure of the synthesis gas is 0.5-10MPa, the reaction temperature is 300-600 DEG CAirspeed of 300-10000h-1(ii) a Synthesis gas H2The molar ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5.
The preparation process of the composite metal oxide comprises the following steps: adding urea, ammonia water and ammonium carbonate into a cerium and zirconium salt precursor, and mixing the mixture in water at room temperature; and aging the mixed solution, taking out, washing, filtering and drying, roasting the obtained solid in an air atmosphere or by adopting a hydrothermal synthesis method, adding a sodium hydroxide solution into a cerium and zirconium salt precursor, crystallizing for a period of time at high temperature and high pressure in a hydrothermal kettle, taking out, filtering, washing, drying, and roasting the obtained solid in an air atmosphere to obtain the composite metal oxide CexZr (1-x) O2.
Soaking metal oxide in one or more of etching agents such as oleic acid, urotropine, ethylenediamine, ammonia water, hydrazine hydrate and the like; heating the suspended matter at 100-150 deg.c for 30-90 min, washing and filtering to obtain metal oxide with great amount of surface oxygen holes in the reaction atmosphere; drying and reducing the filtered substance in an atmosphere of inert gas or a mixture of inert gas and reducing gas, wherein the inert gas is N2One or more of He and Ar, and reducing atmosphere is H2And one or more than two of CO, wherein the volume ratio of the inert gas to the reducing gas in the mixed gas is 100/10-0/100, and the treatment is carried out for 0.5-5 hours at the temperature of 20-350 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the method is different from the traditional technology (MTO for short) for preparing the low-carbon olefin from the methanol, and realizes the direct conversion of the synthesis gas into the low-carbon olefin by a one-step method.
(2) The preparation process of the composite catalyst is simple, and the conditions are mild; the reaction process has high product yield and selectivity, and particularly, CexZr (1-x) O2 oxide is adopted, the microscopic morphology of the oxide is rod-shaped or spherical, preferably rod-shaped, the stability is good, the selectivity of the low-carbon olefin after 650 hours of reaction can be maintained and can still be maintained at 65-73% of that of the low-carbon olefin of C2-C4, meanwhile, the selectivity of the byproduct methane is extremely low (< 15%), and the method has a good application prospect.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
Preparation of catalyst A component
Preparation of (mono) composite metal oxide CexZr (1-x) O2
(1) The samples numbered as metal oxide 3, metal oxide 4, metal oxide 5, metal oxide 8 and metal oxide 9 adopt cerous nitrate and zirconium nitrate as precursors, and then urea, ammonia water and ammonium carbonate are added into the precursors and mixed with each other in water at room temperature; and aging the mixed solution, taking out, washing, filtering and drying, and roasting the obtained solid in an air atmosphere to obtain the metal oxide CexZr (1-x) O2.
(2) The samples numbered as metal oxide 1, metal oxide 2, metal oxide 6 and metal oxide 7 are prepared by a hydrothermal synthesis method, cerium nitrate and zirconium nitrate are used as precursors, sodium hydroxide solution is added into the precursors, the precursors are crystallized in a hydrothermal kettle at high temperature and high pressure for a period of time, then the precursors are taken out and filtered, washed and dried, and the obtained solid is roasted in the air atmosphere to obtain the metal oxide CexZr (1-x) O2.
The sample is ultrasonically mixed with metal oxide at normal temperature by adopting an etching agent such as oleic acid, urotropine, ethylenediamine, ammonia water, hydrazine hydrate and the like, the metal oxide is soaked in the etching agent solution, and the etching agent and the metal oxide form complexation or directly generate reduction reaction;
heating the suspended matter, taking out, washing and filtering to obtain the nanometer metal oxide material with great amount of surface oxygen cavities.
In table 1: the mass ratio of the catalyst to the etchant is 1: 3. The mass ratio of oleic acid to urotropin is 1:1, no solvent is present, the mass ratio of oleic acid to 5 wt.% hydrazine hydrate is 95:5, no solvent is present; specific processing conditions including etchant, temperature, processing time and atmosphere type are shown in table 1.
Drying or dry reduction:
centrifuging or filtering the obtained product, washing with deionized water, drying or drying and reducing in an atmosphere of inert gas or a mixture of inert gas and reducing gas, wherein the inert gas is N2One or more of He and Ar, and reducing atmosphere is H2And one or more than two of CO, wherein the volume ratio of the inert gas to the reducing gas in the drying and reducing mixed gas is 100/10-0/100, the temperature of the drying and reducing treatment is 350 ℃, and the time is 4 hours. Thus obtaining the metal oxide material with the surface rich in oxygen vacancies. Specific samples and their preparation conditions are shown in table 1. Wherein surface oxygen vacancies are defined as (the molar amount of oxygen atoms to the theoretical stoichiometric molar content).
TABLE 1 preparation of Metal oxide materials and their Performance parameters
Secondly, preparation of catalyst B (molecular sieve with CHA and AEL topological structures)
According to n (Al)2O3)/n(P2O5)＝1,n(SiO2)/n(Al2O3)＝0.5,n(TEA)/n(Al2O3)＝2,nH2O/n(Al2O3)＝75。
Mixing pseudo-boehmite with deionized water, adding phosphoric acid, stirring for 1h to obtain a uniform phase, then adding triethylamine, stirring uniformly, finally adding silica sol, aging for 2h to obtain an initial gel, then transferring the initial gel into a high-pressure synthesis kettle, statically crystallizing at 180 ℃ for 24h, quenching, washing, drying, and then roasting at 550 ℃ in a muffle furnace for 6h to obtain the CHA molecular sieve. The corresponding product is in turn defined as CHA 1-4.
According to n (Al)2O3)/n(P2O5)＝1,n(TEAOH)/n(Al2O3)＝1.4,nH2O/n(Al2O3)＝50。
Mixing pseudo-boehmite with deionized water, adding phosphoric acid, stirring for 1h to obtain a uniform phase, then adding tetraethyl ammonium hydroxide, stirring uniformly, aging for 2h to obtain an initial gel, then transferring the initial gel into a high-pressure synthesis kettle, statically crystallizing at 150 ℃ for 72h, then quenching, washing, drying, and then roasting at 550 ℃ in a muffle furnace for 6h to obtain the AEI molecular sieve. The corresponding product is sequentially defined as AEI 1-3;
TABLE 5 preparation of molecular sieves with CHA or AEL topology and their performance parameters
Preparation of catalyst
Adding the catalyst A and the catalyst B in required proportion into a container, realizing the purposes of separation, crushing, uniform mixing and the like by utilizing one or more than two of extrusion force, impact force, shearing force, friction force and the like generated by the high-speed movement of the materials and/or the container, realizing the conversion of mechanical energy, heat energy and chemical energy by regulating the temperature and the carrier gas atmosphere, and further regulating the interaction among different components.
In the physical mixing process, the mixing temperature can be set to be 20-100 ℃, and the mixing can be carried out in the atmosphere or directly in the air, wherein the atmosphere is as follows: a) nitrogen and/or inert gas, b) a mixed gas of hydrogen and nitrogen and/or inert gas, wherein the volume of hydrogen in the mixed gas is 5-50%, c) a mixed gas of CO and nitrogen and/or inert gas, wherein the volume of CO in the mixed gas is 5-20%, d) O2Mixed with nitrogen and/or inert gases, in which O2The volume of the inert gas in the mixed gas is 5-20%, and the inert gas is one or more than two of helium, argon and neon.
Mechanical stirring: in the stirring tank, the catalysts A and B are mixed by a stirring rod, and the mixing degree and the relative distance of the catalysts A and B can be adjusted by controlling the stirring time (5min-120min) and the stirring speed (30-300 r/min).
Ball milling: the grinding material and the catalyst are rolled in a grinding tank at a high speed to generate strong impact and rolling on the catalyst, so that the catalyst A and the catalyst B are dispersed and mixed. The granularity and relative distance of the catalyst can be adjusted by controlling the proportion of the abrasive (the material can be stainless steel, agate and quartz, the size range is 5mm-15mm) and the catalyst (the mass ratio range is 20-100: 1).
A shaking table mixing method: premixing catalysts A and B, and filling the catalyst A and the catalyst B into a container; mixing the catalyst A and the catalyst B by controlling the reciprocating oscillation or the circumferential oscillation of the shaking table; by adjusting the oscillation speed (range: 1-70r/min) and time (range: 5min-120min), uniform mixing is realized and the relative distance is adjusted.
Mechanical grinding method: catalysts a and B were premixed and charged to the vessel. Under a certain pressure (range: 5kg-20kg), the catalyst is relatively moved (speed range: 30-300r/min) with a grinder such as a mechanical/magnetic stirrer, a ball mill, a shaker, an automatic grinder/mortar, etc., to adjust the particle size and relative distance of the catalyst and to achieve uniform mixing.
Specific catalyst preparations and their parametric characteristics are shown in table 6.
TABLE 6 preparation of the catalysts and their parametric characterization
Examples of catalytic reactions
Fixed bed reactions are exemplified, but the catalyst is also suitable for use in moving bed reactors. The device is provided with a gas mass flow meter and an on-line product analysis chromatograph (tail gas of a reactor is directly connected with a quantitative valve of the chromatograph to carry out periodic real-time sampling analysis).
2g of the catalyst of the present invention was placed in a fixed bed reactor, and the air in the reactor was replaced with Ar, followed by H2In the atmosphereThe temperature is raised to 200 ℃, and the synthesis gas (H) is switched2The mol ratio of/CO is 0.2-3.5), the pressure of the synthetic gas is 0.5-10MPa, the temperature is raised to the reaction temperature of 300-. The product was analyzed by on-line chromatographic detection.
The reaction performance can be varied by varying the temperature, pressure and space velocity. After 650h, the selectivity of low-carbon olefin (one or more than two of ethylene, propylene and butylene) in the product can reach 65-73%, and the conversion rate of the raw material is 15-50%; because the surface hydrogenation activity of the catalyst composite metal oxide is not high, the generation of a large amount of methane can be avoided, and the methane selectivity is lower than 15%.
TABLE 7 specific use of the catalyst and the results after 650h of reaction
The prior art is as follows: the catalyst is same as 201610600945.6 patent example J.
Prior art 2: the catalyst is same as Z1 in patent example 201610600945.6.
By way of comparison of the examples, it can be found that the CeZr-containing oxides exhibit a better selectivity in a suitable composition range and in a preferred morphology.
The catalyst of the invention can maintain excellent product selectivity after long-time reaction.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.
Claims (9)
1. The catalyst containing CeZr oxide is prepared by mixing a component A and a component B in a physical mode, wherein the active component of the component A is a composite metal oxide, and is characterized in that: the composite metal oxide is CexZr(1-x)O2The value range of x is 0.6-0.98,the component B is a molecular sieve; the microscopic morphology of the metal oxide is rod-shaped or spherical;
the depth of the composite metal oxide in the direction from the surface of the crystal grain to the inside of the crystal grain is within the range of 0.3nm under the reaction atmosphere, and the surface oxygen vacancy is 40-90 percent;
the component B is a molecular sieve with CHA or AEI topological structure;
the weight ratio of the active component in the component A to the component B is 0.3-5.
2. The CeZr oxide containing catalyst according to claim 1, characterized in that: the composite metal oxide is CexZr(1-x)O2The value range of x is 0.8-0.98; the metal oxide has a rod-like micro-morphology.
3. The CeZr oxide containing catalyst according to claim 1, characterized in that: the depth of the composite metal oxide in the direction from the surface of the crystal grain to the inside of the crystal grain is within the range of 0.3nm under the reaction atmosphere, and the surface oxygen vacancy is 60-90%.
4. The CeZr oxide containing catalyst according to claim 1, characterized in that: a dispersant is selectively added in the component A, and the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2And one or two of ZnO and the composite metal oxide are dispersed in the dispersant, the content of the dispersant in the component A is 0.05-90 wt.%, and the balance is the composite metal oxide.
5. The CeZr oxide containing catalyst according to claim 1, characterized in that: the framework elements of the molecular sieve with the CHA and AEI topological structures comprise one or more than two of Si-Al-O, Ga-Al-O, Ti-Si-O, Si-Al-P-O, Al-P-O, Ge-Al-O.
6. The CeZr oxide containing catalyst according to claim 1, characterized in that: the physical mixing is one or more of mechanical stirring, ball milling, table mixing and mechanical grinding.
7. A method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation is characterized by comprising the following steps: it may contain CO and H2The synthesis gas is raw material gas, conversion reaction is carried out on a fixed bed or a moving bed, and the adopted catalyst is the CeZr oxide-containing catalyst of any one of claims 1 to 6.
8. The method of claim 7, wherein: the synthesis gas is H2Mixed gas of/CO, H2The mol ratio of/CO is 0.2-3.5; the pressure of the synthesis gas is 0.5-10MPa, the reaction temperature is 300-600 ℃, and the space velocity is 300-10000h-1。
9. The method of claim 8, wherein: the synthesis gas is H2Mixed gas of/CO, H2The mol ratio of/CO is 0.3-2.5.
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| CN112108180A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院大连化学物理研究所 | Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof |
| CN110479364A (en) * | 2019-09-02 | 2019-11-22 | 太原理工大学 | A kind of method that bifunctional catalyst and CO add hydrogen directly to convert producing light olefins |
| CN112675904B (en) * | 2019-10-18 | 2023-08-04 | 中国石油化工股份有限公司 | Carbon-containing catalyst and application thereof in one-step method for producing low-carbon olefin by using synthesis gas |
| CN112191278B (en) * | 2020-10-27 | 2023-04-07 | 正大能源材料(大连)有限公司 | Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
| CN114733565B (en) * | 2021-01-07 | 2024-04-02 | 国家能源投资集团有限责任公司 | Composite catalyst, preparation method and application thereof, and method for preparing low-carbon olefin by one-step synthesis gas |
| CN112844362B (en) * | 2021-01-27 | 2023-07-21 | 陕西师范大学 | Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reactions |
| CN114602452B (en) * | 2022-03-15 | 2023-10-17 | 中国科学院赣江创新研究院 | Self-template porous cerium-zirconium solid solution and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074490A (en) * | 2007-06-15 | 2007-11-21 | 北京工业大学 | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes |
| CN101920207A (en) * | 2010-05-10 | 2010-12-22 | 内蒙古大学 | Synthetic gas-to-oil cobalt-based catalyst using cerium-zirconium solid solution as carrier |
| CN106311317A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst and method for directly preparing light olefins from synthesis gas by one-step process |
| CN106345514A (en) * | 2016-07-29 | 2017-01-25 | 厦门大学 | Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof |
| CN106540740A (en) * | 2016-10-28 | 2017-03-29 | 厦门大学 | Catalyst by synthesis gas high selectivity light aromatics and preparation method thereof |
| CN106540674A (en) * | 2016-10-26 | 2017-03-29 | 中科合成油技术有限公司 | A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015084575A2 (en) * | 2013-12-06 | 2015-06-11 | Exxonmobil Chemical Patents Inc. | Production of c2+ olefins |
-
2017
- 2017-11-08 CN CN201711089864.5A patent/CN109745965B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074490A (en) * | 2007-06-15 | 2007-11-21 | 北京工业大学 | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes |
| CN101920207A (en) * | 2010-05-10 | 2010-12-22 | 内蒙古大学 | Synthetic gas-to-oil cobalt-based catalyst using cerium-zirconium solid solution as carrier |
| CN106311317A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst and method for directly preparing light olefins from synthesis gas by one-step process |
| CN106345514A (en) * | 2016-07-29 | 2017-01-25 | 厦门大学 | Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof |
| CN106540674A (en) * | 2016-10-26 | 2017-03-29 | 中科合成油技术有限公司 | A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized |
| CN106540740A (en) * | 2016-10-28 | 2017-03-29 | 厦门大学 | Catalyst by synthesis gas high selectivity light aromatics and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Direct and Highly Selective Conversion of Synthesis Gas into Lower Olefins: Design of a Bifunctional Catalyst Combining Methanol Synthesis and Carbon–Carbon Coupling;Qinghong Zhang et al.;《Angewandte Chemie》;20160309;第55卷(第15期);第4728页结论和实验部分 * |
| Selective conversion of syngas to light olefins;Pan Xiulian et al.;《Science》;20160304;第351卷(第6277期);第1065-1068页 * |
| 合成气催化转化直接制备低碳烯烃研究进展;于飞;《燃料化学学报》;20160731;第44卷(第7期);第801-814页 * |
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