CN107913729B - Composite catalyst and preparation method thereof - Google Patents
Composite catalyst and preparation method thereof Download PDFInfo
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- CN107913729B CN107913729B CN201610880522.4A CN201610880522A CN107913729B CN 107913729 B CN107913729 B CN 107913729B CN 201610880522 A CN201610880522 A CN 201610880522A CN 107913729 B CN107913729 B CN 107913729B
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- C07C1/04—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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- 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
Abstract
The present invention relates to the methods of composite catalyst and preparation method thereof and synthesis gas production low-carbon alkene, mainly solve the problems, such as that CO conversion ratio is low low with selectivity of light olefin in one-step method from syngas reaction for preparing light olefins existing in the prior art.Present invention use, composite catalyst include following components: a) 1~20% ferro element or its oxide by weight percentage；B) 1~15% Ce elements or its oxide；C) 1~15% be selected from least one of magnesium and calcium element or its oxide；D) 2~10% neodymium element or its oxide；E) 20~75% silica；F) technical solution of 20~40% modified zsm-5 zeolite, preferably solves the problems, such as this, can be used for the industrial production of synthesis gas preparing low-carbon olefins.
Description
Technical field
The present invention relates to composite catalyst and its preparation method and application, more particularly to a kind of low-carbon alkene that produces
Composite catalyst and its preparation method and application.
Background technique
Low-carbon alkene refers to the alkene that carbon atom number is less than or equal to 4.Using ethylene, propylene as the low-carbon alkene right and wrong of representative
Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for answering
It asks.Currently, the petrochemical industry route that the production of low-carbon alkene mainly uses lighter hydrocarbons (ethane, naphtha, light diesel fuel) to crack, due to
The long-term run at high level of growing lack and crude oil price of Global Oil resource develops low-carbon alkene industry and relies solely on petroleum light hydrocarbon
Increasing raw material problem can be encountered for the tube cracking furnace technique of raw material, low-carbon alkene production technology and raw material must be polynary
Change.The direct preparing low-carbon olefins of one-step method from syngas be exactly carbon monoxide and hydrogen under the action of catalyst, it is anti-by F- T synthesis
The process of low-carbon alkene of the carbon atom number less than or equal to 4 should directly be made, which is not necessarily to as indirect method technique from conjunction
At gas through methanol or dimethyl ether, alkene is further prepared, simplification of flowsheet greatly reduces investment.Petroleum resources are short at home
It lacks, it is current that external dependence degree is higher and higher, international oil price constantly rises violently, selects synthesis gas producing olefinic hydrocarbons technique that can widen former material
Expect source, synthesis gas will be produced by raw material of crude oil, natural gas, coal and recyclable materials, it can be for based on high cost feedstocks
As naphtha steam cracking technology in terms of provide alternative solution.The coal price of China coal resources and relative moderate abundant
It is refined oil for Development of Coal and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And it is abundant in Natural Gas In China
Oil gas field near, if Gas Prices are cheap, and application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy
Using China's coal abundant and natural gas resource, pass through gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), hair
The substitute energy source for petroleum technology of preparation of low carbon olefines by synthetic gas is opened up, will be of great significance to energy problem, China is solved.
One-step method from syngas producing light olefins technique functions are derived from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic
Carbon number distribution defer to ASF distribution, each hydro carbons all has that theoretical maximum is selective, such as C2-C4The selectivity of fraction is up to
57%, gasoline fraction (C5-C11) selectivity be up to 48%.Chain growth probability α value is bigger, and the selectivity of product heavy hydrocarbon is got over
Greatly.Once α value has determined, the selectivity of entire synthetic product is determined that, chain growth probability α value depend on catalyst composition,
Granularity and reaction condition etc..In recent years, it has been found that due to alkene secondary counter caused by alhpa olefin adsorbing again on a catalyst
It answers, product distribution is distributed away from ideal ASF.F- T synthesis is a kind of strong exothermal reaction, and a large amount of reaction heat will promote catalyst
Carbon deposit reaction is easier to generate methane and low-carbon alkanes, leads to selectivity of light olefin sharp fall；Secondly, complicated power
It is unfavorable that factor is also caused to selectivity synthesis low-carbon alkene；The ASF distribution of Fischer-Tropsch synthetic limits synthesizing low-carbon alkene
Selectivity.The catalyst of F- T synthesis gas producing light olefins is mainly iron catalyst series, is directly made to improve synthesis gas
The selectivity of low-carbon alkene is taken, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, as being suitable for using molecular sieve
Cellular structure is conducive to low-carbon alkene and diffuses out metal active centres in time, inhibits the secondary response of low-carbon alkene；Improve gold
Belong to ion dispersibility, also there is preferable olefine selective；Support-metal strong interaction change can also be improved low-carbon alkene choosing
Selecting property；The suitable transition metal of addition, can be enhanced the bond energy of active component and carbon, and methane is inhibited to generate, and improve low-carbon alkene
Selectivity；Electronics accelerating auxiliaries are added, CO chemisorption heat is promoted to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, as a result
Selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be inhibited, improve its selectivity.
By the Support effect and the certain transition metal promoters of addition and alkali metal promoter of catalyst carrier, catalyst performance can obviously improve
Can, develop the fischer-tropsch synthetic catalyst of the highly selective producing light olefins of novel high-activity with the non-ASF distribution of product.
Synthesis gas directly produces low-carbon alkene, it has also become one of the research hotspot of fischer-tropsch synthetic catalyst exploitation.The Chinese Academy of Sciences
In patent CN1083415A disclosed in Dalian Chemical Physics Research Institute, with the Group IIAs such as MgO alkali metal oxide or silica-rich zeolite point
Iron-Mn catalyst system that son sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent with highly basic K or Cs ion, in synthesis of gas produced low-carbon alkene
Hydrocarbon reaction pressure is 1.0~5.0MPa, at 300~400 DEG C of reaction temperature, can get higher active (CO conversion ratio 90%) and
Selectivity (selectivity of light olefin 66%).But the catalyst preparation process is complicated, the especially preparation of carrier zeolite molecular sieve
Forming process higher cost, is unfavorable for industrialized production.In the number of patent application 01144691.9 that Beijing University of Chemical Technology is declared,
Laser pyrolysis processes combination solid phase reaction combination technique is used to be prepared for Fe3Fe base nano-catalyst based on C is applied to synthesis
Gas producing light olefins, and good catalytic effect is achieved, due to needing using laser pyrolysis technology, preparation process is more numerous
Trivial, raw material uses Fe (CO)5, catalyst cost is very high, and industrialization is difficult.The patent that Beijing University of Chemical Technology is declared
In ZL03109585.2, using vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. is the Fe/ activated-carbon catalyst of auxiliary agent for closing
At gas reaction for preparing light olefins, under conditions of no unstripped gas recycles, CO conversion ratio 96%, low-carbon alkene is in hydrocarbon
Selectivity 68%.The molysite and auxiliary agent manganese salt that the catalyst preparation uses are more expensive and less soluble ferric oxalate and acetic acid
Manganese, while with ethanol as solvent, just unavoidably increase the cost of material and operating cost of catalyst preparation process.It is further
The cost for reducing catalyst, in its number of patent application 200710063301.9, catalyst uses common drug and reagent system
It is standby, the molysite used be ferric nitrate, manganese salt is manganese nitrate, and sylvite is potassium carbonate, and active carbon is coconut husk charcoal, can catalyst must flow
High-temperature roasting and Passivation Treatment are carried out under dynamic nitrogen protection, needs special installation, preparation process is complicated, higher cost.And it is above-mentioned
Catalyst CO conversion ratio in the fixed bed reaction and selectivity of light olefin are lower.
Summary of the invention
The first technical problem to be solved by the present invention is that synthesis gas produces in low-carbon alkene technology CO turns in the prior art
The low problem low with selectivity of light olefin in product of rate, provides composite catalyst, which produces for synthesis gas
When low-carbon alkene reacts, have the advantages that selectivity of light olefin is high in CO high conversion rate and product.
The second technical problem to be solved by the present invention is to provide the preparation method of the catalyst of one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is to provide the synthesis gas of the catalyst using one of above-mentioned technical problem
The method for producing low-carbon alkene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: composite catalyst, with weight hundred
Dividing than meter includes following components:
A) 1~20% ferro element or its oxide；
B) 1~15% Ce elements or its oxide；
C) 1~15% be selected from least one of magnesium and calcium element or its oxide；
D) 2~10% neodymium element or its oxide；
E) 20~75% silica；
F) 20~40% modified zsm-5 zeolite, including following components in terms of the parts by weight of modified zsm-5 zeolite
(1) 1~10% part of gallium element or its oxide；(2) 90~99% parts of ZSM-5 molecular sieves.
In above-mentioned technical proposal, the oxide of iron is preferably di-iron trioxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of ferro element or its oxide content is 5
~15%.
In above-mentioned technical proposal, the oxide of Cerium in Catalysts is preferably ceria.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of Ce elements or its oxide content is 1
~10%.
In above-mentioned technical proposal, the oxide of magnesium and calcium is respectively magnesia and calcium oxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, at least one of magnesium and calcium element or its oxide
The preferred scope of content is 1~10%.
In above-mentioned technical proposal, the oxide of neodymium is neodymium oxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of neodymium element or its oxide content is 2
~8%.
In above-mentioned technical proposal, silica described in catalyst, in terms of catalyst weight percent, content it is preferred
Range is 20~60%.
In above-mentioned technical proposal, the silica alumina ratio preferred scope of ZSM-5 molecular sieve described in catalyst is 200~600.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The preparation of the composite catalyst described in any one of case, comprising the following steps:
(1) soluble in water that mixed solution A is made by molysite, cerium salt, magnesium salts or calcium salt, neodymium salt；
(2) mixed solution A is mixed to obtain to catalyst precarsor B with silica；
(3) it by catalyst precarsor B, roasts after drying, obtains required Fischer-Tropsch synthetic iron-based catalyst C.
(4) solution D is made by gallium salt is soluble in water；
(5) solution D is mixed to obtain to catalyst precarsor E with ZSM-5 molecular sieve；
(6) it by catalyst precarsor E, roasts after drying, obtains required ZSM-5 Type Zeolites agent F.
(7) Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F are mixed to get required compound
Catalyst.
In above-mentioned technical proposal, the hybrid mode of step (2) and/or step (5) is not specially required, but in vacuum condition
Lower mixed effect is especially good.Solution is such as, but not limited to impregnated into corresponding solid component under the conditions of 1~80kPa of vacuum degree.
After in above-mentioned technical proposal, the hybrid mode of step (7) is not specially required, but mill is mixed in the ball mill, tabletting
Molding, further crushing and screening effect are especially good.
In above-mentioned technical proposal, the preferred scope of the maturing temperature in step (3) is 700~900 DEG C, calcining time it is excellent
Selecting range is 2.0~8.0 hours；The preferred scope of maturing temperature in step (6) be 400~600 DEG C, calcining time it is preferred
Range is 2.0~6.0 hours.
To solve above-mentioned technical problem three, technical scheme is as follows: the method that synthesis gas produces low-carbon alkene,
Using synthesis gas as raw material, H2It is 1~3 with the molar ratio of CO, is 250~400 DEG C in reaction temperature, reaction pressure is 1.0~
3.0Mpa, feed gas volume air speed are 500~5000h-1Under conditions of, the technical solution of one of unstripped gas and above-mentioned technical problem
Any one of described in composite catalyst haptoreaction generate C2~C4Alkene.
The method of the present invention use Fischer-Tropsch synthetic iron-based catalyst by vacuum impregnation technology prepare, can make active component with
Auxiliary agent high uniformity is scattered in carrier surface, increases the quantity for being exposed to the active sites of carrier surface, improves the conversion ratio of CO；Subtract
The partial size of small active component and auxiliary agent improves selectivity of light olefin.The gallium modified zsm-5 zeolite of use passes through vacuum impregnation
Method preparation, is conducive to gallium element in the evenly dispersed of ZSM-5 molecular sieve channel surfaces, reduces the surface acidity of ZSM-5 molecular sieve.
Transition metal Ce, alkaline-earth metal Mg or Ca are introduced in the Fischer-Tropsch synthetic iron-based catalyst that the method for the present invention uses, with
And rare earth metal Nd is conducive to improve the CO conversion ratio of catalyst and the selectivity of low-carbon alkene as catalyst promoter.Especially
It is to introduce rare earth metal Nd to be released effectively the activity of catalyst due to the interaction between Nd and active component and auxiliary agent,
Improve the conversion ratio of CO and the selectivity of low-carbon alkene.
The method of the present invention is mixed with compound catalysis using Fischer-Tropsch synthetic iron-based catalyst and modified zsm-5 zeolite
On the one hand agent produces low-carbon alkene using fischer-tropsch synthetic catalyst high-activity high-selectivity, on the other hand utilize modified ZSM-5 point
The splitting action of son sieve, the long chain hydrocarbons catalytic pyrolysis that Fischer-Tropsch reaction is generated further increase low-carbon at small molecule low-carbon alkene
Olefine selective.
The use condition of the catalyst is as follows: with H2Synthesis gas with CO composition is raw material, H2With the molar ratio of CO be 1~
3, it is 250~400 DEG C in reaction temperature, reaction pressure is 1.0~3.0Mpa, and feed gas volume air speed is 500~2500h-1's
Under the conditions of, unstripped gas is contacted with catalyst, and achieve preferable technical effect: CO conversion ratio compares the prior art up to 99.7%
Improve 3.7%；Selectivity of the low-carbon alkene in hydrocarbon improves 10.1% up to 78.1%, than the prior art, more in detail
Thin result is seen attached list.
The present invention is described further for the following examples, and protection scope of the present invention is not by these embodiments
Limitation.
Specific embodiment
[embodiment 1]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 2]
Weigh 5.1 grams of Fe(NO3)39H2Os, 2.5 gram of six nitric hydrate cerium, 6.4 grams of magnesium nitrate hexahydrates, 5.2 gram of six hydration
Neodymium nitrate is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixed solution
A is impregnated in 75.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, so
After roasted, 700 DEG C of maturing temperature, calcining time 8h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 4.5 gram of nine hydration
Gallium nitrate is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 19.0 grams of silica alumina ratios are 400；Impregnated catalyst precarsor E is in 120 DEG C of conditions
Lower drying, is then roasted, 500 DEG C of maturing temperature, calcining time 4h to get arrive ZSM-5 Type Zeolites agent F.It will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst includes following components by weight percentage:
1%Fe2O3, 1%CeO2, 1%MgO, 2%Nd2O3, 75%SiO2, 1.0%Ga2O3, 19.0%ZSM-5；It is made compound to urge
Agent carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 3]
Weigh 101.2 grams of Fe(NO3)39H2Os, 25.2 gram of six nitric hydrate cerium, 29.3 grams of calcium nitrate, 26.1 gram of six hydration
Neodymium nitrate is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixed solution
A is impregnated in 20.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, so
After roasted, 900 DEG C of maturing temperature, calcining time 2h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 gram of nine hydration
Gallium nitrate is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400；Impregnated catalyst precarsor E is in 120 DEG C of conditions
Lower drying, is then roasted, 500 DEG C of maturing temperature, calcining time 4h to get arrive ZSM-5 Type Zeolites agent F.It will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst includes following components by weight percentage:
20%Fe2O3, 10%CeO2, 10%CaO, 10%Nd2O3, 20%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 4]
Weigh 25.3 grams of Fe(NO3)39H2Os, 37.8 gram of six nitric hydrate cerium, 95.4 grams of magnesium nitrate hexahydrates, 26.1 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 35.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 4.5 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 19.0 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 400 DEG C of maturing temperature, calcining time 6h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 5%Fe2O3, 15%CeO2, 15%MgO, 10%Nd2O3, 35%SiO2, 1.0%Ga2O3, 19.0%ZSM-5；Made answers
Mould assembly catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 5]
Weigh 75.9 grams of Fe(NO3)39H2Os, 2.5 gram of six nitric hydrate cerium, 2.9 grams of calcium nitrate, 5.2 gram of six nitric hydrate
Neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned mixed solution A is soaked
Stain is in 41.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, then into
Row roasting, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 8.9 gram of nine nitric hydrate
Gallium is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in 38.0
On the ZSM-5 molecular sieve that gram silica alumina ratio is 400 catalyst precarsor E；Impregnated catalyst precarsor E is done under the conditions of 120 DEG C
It is dry, then roasted, 600 DEG C of maturing temperature, calcining time 2h to get arrive ZSM-5 Type Zeolites agent F.By Fischer-Tropsch
After synthesis iron base catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding is crushed
Screening obtains required composite catalyst.Obtained composite catalyst includes following components: 15% by weight percentage
Fe2O3, 1%CeO2, 1%CaO, 2%Nd2O3, 41%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made composite catalyst
Synthesis gas production low-carbon alkene reaction is carried out under certain condition, and experimental result is listed in table 1.
[embodiment 6]
Weigh 101.2 grams of Fe(NO3)39H2Os, 37.8 gram of six nitric hydrate cerium, 95.4 grams of magnesium nitrate hexahydrates, 18.2 grams
Six nitric hydrate neodymiums are dissolved in 30.0 grams of deionized waters and mixed solution A are made；It, will be above-mentioned mixed under conditions of vacuum degree 80kPa
It closes solution A and is impregnated in 20.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 5.4 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 21.8 grams of silica alumina ratios are 200 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 20%Fe2O3, 15%CeO2, 15%MgO, 7%Nd2O3, 20%SiO2, 1.2%Ga2O3, 21.8%ZSM-5；Made answers
Mould assembly catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 7]
Weigh 5.1 grams of Fe(NO3)39H2Os, 12.6 gram of six nitric hydrate cerium, 14.6 grams of calcium nitrate, 5.2 gram of six nitric hydrate
Neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned mixed solution A is soaked
Stain is in 60.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, then into
Row roasting, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.2 gram of nine nitric hydrate
Gallium is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in 25.6
On the ZSM-5 molecular sieve that gram silica alumina ratio is 600 catalyst precarsor E；Impregnated catalyst precarsor E is done under the conditions of 120 DEG C
It is dry, then roasted, 500 DEG C of maturing temperature, calcining time 4h to get arrive ZSM-5 Type Zeolites agent F.By Fischer-Tropsch
After synthesis iron base catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding is crushed
Screening obtains required composite catalyst.Obtained composite catalyst includes following components: 1% by weight percentage
Fe2O3, 5%CeO2, 5%CaO, 2%Nd2O3, 60%SiO2, 1.4%Ga2O3, 25.6%ZSM-5；Made composite catalyst
Synthesis gas production low-carbon alkene reaction is carried out under certain condition, and experimental result is listed in table 1.
[embodiment 8]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 23.4 grams of calcium nitrate, 13.0 gram of six hydration nitre
Sour neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixed solution A
It is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, then
Roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 gram of nine hydration nitre
Sour gallium is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 300；Impregnated catalyst precarsor E is in 120 DEG C of conditions
Lower drying, is then roasted, 500 DEG C of maturing temperature, calcining time 4h to get arrive ZSM-5 Type Zeolites agent F.It will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst includes following components by weight percentage:
10%Fe2O3, 7%CeO2, 8%CaO, 5%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；It is made compound to urge
Agent carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 9]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 1.3 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 29.7 grams of silica alumina ratios are 500 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 0.3%Ga2O3, 29.7%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 10]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 9.4 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 27.9 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 2.1%Ga2O3, 27.9%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 11]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 13.4 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 27.0 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 3.0%Ga2O3, 27.0%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[embodiment 12]
Catalyst made from Example 1, other are constant, only change reaction condition, carry out synthesis gas and produce low-carbon alkene,
Experimental result is listed in table 2.
[comparative example 1]
50.6 grams of Fe(NO3)39H2Os, 25.2 gram of six nitric hydrate cerium are weighed, 63.6 grams of magnesium nitrate hexahydrates are dissolved in 30.0
Mixed solution A is made in gram deionized water；Under conditions of vacuum degree 80kPa, above-mentioned mixed solution A is impregnated in 40.0 grams
SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is dry under the conditions of 120 DEG C, is then roasted, and roasts
Burn 800 DEG C of temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.6.7 gram of nine nitric hydrate gallium is weighed, is dissolved in
Solution D is made in 10.0 grams of deionized waters；Under conditions of vacuum degree 80kPa, above-mentioned solution D is impregnated in 28.5 grams of silica alumina ratios
To obtain catalyst precarsor E on 400 ZSM-5 molecular sieve；Impregnated catalyst precarsor E is dry under the conditions of 120 DEG C, then into
Row roasting, 500 DEG C of maturing temperature, calcining time 4h to get arrive ZSM-5 Type Zeolites agent F.It is urged Fischer-Tropsch synthetic iron-based
After agent C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding, crushing and screening obtains institute
The composite catalyst needed.Obtained composite catalyst includes following components: 10%Fe by weight percentage2O3, 10%
CeO2, 10%MgO, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made composite catalyst under certain condition into
Row synthesis gas produces low-carbon alkene reaction, and experimental result is listed in table 1.
[comparative example 2]
Weigh 50.6 grams of Fe(NO3)39H2Os, 10.1 gram of six nitric hydrate cerium, 25.4 grams of magnesium nitrate hexahydrates, 31.3 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 4%CeO2, 4%MgO, 12%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
[comparative example 3]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 30 grams of silicon
Aluminium is drier under the conditions of 120 DEG C than the ZSM-5 molecular sieve for 400, is then roasted, 500 DEG C of maturing temperature, calcining time
4h.By Fischer-Tropsch synthetic iron-based catalyst C and after the mixing of modified ZSM-5 molecular sieve, after mill is mixed in the ball mill, tabletting at
Type, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 30%ZSM-5；Made composite catalyst is one
Synthesis gas production low-carbon alkene reaction is carried out under fixed condition, experimental result is listed in table 1.
[comparative example 4]
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum degree 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；Impregnated catalyst precarsor B is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of maturing temperature, calcining time 5h to get arrive Fischer-Tropsch synthetic iron-based catalyst C.Weigh 16.1 grams
Nine nitric hydrate galliums are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum degree 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 26.4 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；Impregnated catalyst precarsor E is 120
It is dry under the conditions of DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Molding, crushing and screening obtain required composite catalyst.Obtained composite catalyst includes with the following group by weight percentage
Point: 10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 3.6%Ga2O3, 26.4%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
The reducing condition of above-described embodiment and comparative example are as follows:
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3ml
Catalyst loading 2000 hours-1
Also Primordial Qi H2
Recovery time 12 hours
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 2000 hours-1
Raw material proportioning (mole) H2/ CO=2.5/1
Table 1
Table 2
* the evaluation condition changed described in the table 1 compared with condition.
Claims (9)
1. composite catalyst includes following components by weight percentage:
A) oxide of 1~20% iron；
B) oxide of 1~15% cerium；
C) at least one of the oxide of 1~15% oxide and calcium selected from magnesium；
D) oxide of 2~10% neodymium；
E) 20~75% silica；
F) 20~40% modified zsm-5 zeolite, including following components (1) 1 in terms of the parts by weight of modified zsm-5 zeolite
The oxide of~10% part of gallium；(2) 90~99% parts of ZSM-5 molecular sieves.
2. composite catalyst according to claim 1, it is characterised in that the oxide of iron is three in the catalyst
Aoxidize two iron.
3. composite catalyst according to claim 1, it is characterised in that the oxide of the Cerium in Catalysts is two
Cerium oxide.
4. composite catalyst according to claim 1, it is characterised in that the oxide and calcium of magnesium in the catalyst
Oxide be respectively magnesia and calcium oxide.
5. composite catalyst according to claim 1, it is characterised in that the oxide of neodymium is three in the catalyst
Aoxidize two neodymiums.
6. composite catalyst according to claim 1, it is characterised in that silica in the catalyst, with catalysis
Agent weight percent meter, content are 20~60%.
7. composite catalyst according to claim 1, it is characterised in that the silicon of ZSM-5 molecular sieve in the catalyst
Aluminium ratio is 200~600.
8. the preparation method of the described in any item composite catalysts of claim 1~7, comprising the following steps:
(1) soluble in water that solution A is made by molysite, cerium salt, magnesium salts or calcium salt, neodymium salt；
(2) mixed solution A is mixed to obtain to catalyst precarsor B with silica；
(3) it by catalyst precarsor B, roasts after drying, obtains required Fischer-Tropsch synthetic iron-based catalyst C；
(4) solution D is made by gallium salt is soluble in water；
(5) solution D is mixed to obtain to catalyst precarsor E with ZSM-5 molecular sieve；
(6) it by catalyst precarsor E, roasts after drying, obtains required ZSM-5 Type Zeolites agent F；
(7) Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F are mixed to get required compound catalysis
Agent.
9. the method that synthesis gas produces low-carbon alkene, using synthesis gas as raw material, H2Molar ratio with CO is 1~3, in reaction temperature
It is 250~400 DEG C, reaction pressure is 1.0~3.0MPa, and feed gas volume air speed is 500~5000h-1Under conditions of, unstripped gas
C is generated with the described in any item composite catalyst haptoreactions of claim 1~72~C4Alkene.
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| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN103521259A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparation of olefine from synthesis gas and preparation method thereof |
| CN104226329A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN103521259A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparation of olefine from synthesis gas and preparation method thereof |
| CN104226329A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof |
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