CN103962169B - It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed - Google Patents
It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed Download PDFInfo
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- CN103962169B CN103962169B CN201310040880.0A CN201310040880A CN103962169B CN 103962169 B CN103962169 B CN 103962169B CN 201310040880 A CN201310040880 A CN 201310040880A CN 103962169 B CN103962169 B CN 103962169B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 241000219782 Sesbania Species 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- -1 Ethylene, propylene, butadiene Chemical class 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- YXIZUXGMHQUZQH-UHFFFAOYSA-N diazanium hydrogen carbonate Chemical compound [NH4+].[NH4+].OC([O-])=O.OC([O-])=O YXIZUXGMHQUZQH-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of method for preparing catalyst, the method comprising the steps of:(1) 5 molecular sieves of ZSM, host material, binding agent and water are mixed, is configured to aqueous slurry, is counted on the basis of the gross weight of the aqueous slurry, wherein the total content of component in addition to water is 20 50 weight %;(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained;(3) roasting is carried out to graininess intermediate product obtained in step (2), the catalyst for alkene is prepared by methanol in fluid bed is obtained.Present invention also offers by obtained in methods described catalyst and the method that alkene is prepared by methanol in fluid bed using the catalyst.
Description
Technical field
The present invention relates generally to catalytic field, more particularly, the present invention relates to it is a kind of for fluidized-bed reactor by
Methanol prepares catalyst of alkene and preparation method thereof.
Background technology
Ethylene, propylene, butadiene are important industrial chemicals, are usually obtained from naphtha pyrolysis and steam cracking,
Another main source of propylene is ethylene propylene simultaneously and refinery's by-product propylene, but these modes of production are difficult to meet China's day
The demand to propylene that benefit increases, China from resource distribution for many coals and few oil, methanol device production capacity surplus, Devoting Major Efforts To Developing
The technology of methanol-to-olefins has very important economy and social meaning.It has been reported that various methanol-to-olefins technique
In, with ZSM-5 molecular sieve as catalyst, people have been now subjected to using the MTP technologies that methanol is Material synthesis alkene great
Pay attention to.
German LURGI develops methanol-to-olefins bed technology(WO2004/018089), it is public using southern chemistry
The ZSM-5 molecular sieve catalyst of department and fixed bed reactors carry out methanol to olefins reaction, and Propylene Selectivity is 35~40%,
CN102531823A, CN101172918B, CN101279280B, CN101402049A, CN102211971A are also disclosed respectively
The technique and method for preparing catalyst of preparing propylene from methanol are carried out using fixed bed reactors, mainly with ZSM-5 molecular sieve as work
Property component, which is carried out it is various modified, so as to improve the one way selectivity of propylene.But the reaction of methanol-to-olefins is strongly exothermic
Reaction, in the case of using fixed bed reactors, in laboratory stage, due to loaded catalyst it is fewer, and water/alcohol
Than high, unnecessary heat can be removed by the water in reaction system.And after industrial amplification is carried out, fixed bed reactors are passed
The feature of hot property difference is just highlighted at once, bad due to radiating, and can there are many overheated areas in fixed bed reactors
Domain, catalyst are easy to as bed temperature is too high and coking and deactivation.In order to solve this problem, people take some and trade off
Additional step.For example, at present, in the strange MTP technologies in industrialized Shandong, methanol feedstock first passes through dimethyl ether reactor,
Methanol/dimethyl ether gaseous mixture is wherein converted into, MTP fixed beds is then entered back into and is reacted.In addition, in order to promote heat transfer,
Reaction gas is uniformly divided into six sections in fixed bed reactors to enter in multi-layer fixed-bed reactor.Above measure is substantially increased
Process complexity and operation cost.Even if in addition, in the case where these measures are taken, the heat transfer property of fixed bed reactors is still
Desirable level is not fully reached so, the yield of propylene is extremely difficult to preferable level.
Poor in order to solve the problems, such as fixed bed reactors conductivity of heat, fluid bed is a kind of highly desirable selection, and fluid bed is anti-
The heat transfer property of system is answered to be significantly better than fixed bed.But, fluidized-bed reactor is to the shape of catalyst, granule strength and wear-resisting
Property require it is higher, the intensity and wearability of the fixed bde catalyst above with reference to described in document is poor, and its shape stream
It is difficult to be fluidized in changing bed, therefore develops a kind of cheap, high catalytic activity and the catalysis with high intensity and high-wearing feature
Agent, is the bottleneck of current methanol-to-olefins fluidized-bed process exploitation.
Studies have reported that it is a kind of in fluid bed by methanol-to-olefin catalyst technology of preparing, the technology uses
ZSM-5 molecular sieve is active component, and the component such as addition rare-earth modifier, basic modifier is applied with improving the activity of molecular sieve
The methanol-to-olefins fluidized-bed reaction that the catalyst is carried out reaches the Propylene Selectivity of highest 55%, but this kind of catalyst preparation work
Skill is complicated, relatively costly, and strength ratio is relatively low, still unsatisfactory.Therefore, those skilled in the art are in the urgent need to opening
Send out a kind of with high catalytic activity, high intensity, high-wearing feature cheap catalyst, for carrying out in fluidized-bed reaction system
The reaction of alkene is prepared by methanol.
The content of the invention
In order to solve the above problems, the present invention using ZSM-5 molecular sieve be active component, wherein add host material,
Binding agent, pore creating material and dispersant, are prepared by the forming method being spray-dried anti-for the fluid bed of methanol-to-olefins
Catalyst is answered, this kind of catalyst preparation process is simple, low cost, compares with fixed bed MTP technology, it is not necessary to pre- using dimethyl ether
Reactor, it is possible to use the methanol aqueous solution or methanol of low water alcohol ratio is directly entered fluidized-bed reactor as raw material to be carried out instead
Should.The catalyst of the present invention has splendid intensity and wearability, and after reacting 200h in fluid bed, propylene still has very high
Yield.
In the first aspect of the invention, there is provided a kind of method for preparing catalyst, the catalyst is to use
In the catalyst for being prepared alkene in fluid bed by methanol, the method comprising the steps of:
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, is configured to aqueous slurry, it is aqueous with this
Count on the basis of the gross weight of serosity, wherein the total content of component in addition to water is 20-50 weight %;
(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained;
(3) roasting is carried out to graininess intermediate product obtained in step (2), is obtained for being prepared by methanol in fluid bed
The catalyst of alkene.
In an embodiment of the invention, on the basis of the gross weight of the component in the serosity in addition to water
Meter, in the serosity, the content of ZSM-5 molecular sieve is 20-55 weight %, and the silica alumina ratio of the ZSM-5 molecular sieve is Si/Al=
20-400, preferred 200-400.
In yet another embodiment of the present invention, on the basis of the gross weight of the component in the serosity in addition to water
Meter, the content of host material described in the serosity is 20-59 weight %, and the particle diameter of the host material is less than 2 microns, is selected from
One or more in following material:Kaolin, calcined kaolin, kieselguhr, boehmite, montmorillonite.
In yet another embodiment of the present invention, on the basis of the gross weight of the component in the serosity in addition to water
Meter, the content of binding agent described in the serosity is 20-50 weight %, the one kind or many of the binding agent in the following material
Kind:Alkaline silica sol, acidic silicasol, Alumina gel, aluminum phosphate.
In yet another embodiment of the present invention, the serosity also includes pore creating material.Preferably, the pore creating material is selected from
One or more in following material:Sesbania powder, polyvinyl alcohol, methylcellulose, with the group in the serosity in addition to water
Count on the basis of the gross weight divided, the content of pore creating material described in the serosity is 0.01-1 weight %.In another preferred reality
Apply in mode, the serosity also includes dispersant, one or more in following material of the dispersant:N-octyl alcohol, carbon
Sour hydrogen ammonium, bicarbonate diammonium, are counted on the basis of the gross weight of the component in the serosity in addition to water, are disperseed in the serosity
The content of agent is 0.01-1 weight %.
In yet another embodiment of the present invention, in the step (2), using atomizer exsiccator or pressure type
Spray dryer is spray-dried, and the inlet temperature of spray dryer is 250-300 DEG C, and outlet temperature is 150-200 DEG C, slurry
It is 100-500ml/min that liquid is input into the feed rate of the spray dryer;In the step (3), 400-600 DEG C, it is excellent
Select.
Another aspect of the present invention provides a kind of catalyst prepared by method of the present invention, is urged with described
On the basis of the gross weight of agent count, the catalyst comprising 25-60 weight %, the ZSM-5 molecular sieve of preferred 25-40 weight %,
20-50 weight %, the component and 10-45 weight % from the host material of preferred 30-45 weight %, preferred 25-40
The component from the binding agent of weight %, the particle diameter of the catalyst is 50-110 microns.
The third aspect of the invention provides a kind of method for preparing alkene by methanol, and the method includes, be enough to make
Methanol be converted under the reaction condition of alkene, in a fluidized bed reactor so that the aqueous solution of methanol or methanol with by this
Catalyst prepared by the method for invention is contacted, and the reaction condition is:Methanol quality air speed 0.5-5h-1, reaction temperature 430-
550 DEG C, reaction pressure 0-1MPa.
Specific embodiment
" scope " disclosed herein is in the form of lower limit and the upper limit.One or more lower limits, and one can be respectively
Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower limit and upper limit limit
The border of special scope is determined.The all scopes that can be defined by this way be comprising and can be combined, i.e., any lower limit
Can combine to form a scope with any upper limit.For example, the scope of 60-120 and 80-110 is listed for special parameter, is managed
The scope solved as 60-110 and 80-120 is also what is expected.If additionally, the minimum zone value 1 and 2 listed, and if listed
Maximum magnitude value 3,4 and 5, then following scope can all expect:1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numerical range " a-b " represents the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numerical range " 0-5 " is represented
Whole real numbers, " 0-5 " are that the breviary of these combinations of values is represented.
If be not specifically stated, the term " two kinds " used by this specification refers to " at least two ".
In the present invention, if special explanation, all embodiments mentioned in this article and the side of being preferable to carry out
Formula can be mutually combined to form new technical scheme.
In the present invention, if not special illustrate, all technical characteristics mentioned in this article and preferred feature can
New technical scheme to be formed to be mutually combined.
In the present invention, if not special illustrate, all steps mentioned in this article sequentially can be carried out, it is also possible to
Carry out at random, it is preferred that order is carried out.For example, methods described includes step (a) and (b), represents that methods described can be wrapped
Include (a) and (b) the step of order is carried out, it is also possible to the step of carrying out including order (b) and (a).For example, it is described to mention the side
Method may also include step (c), represent that step (c) can be added to methods described with random order, and for example, methods described can include
Step (a), (b) and (c), may also comprise step (a), (c) and (b), it is also possible to including step (c), (a) and (b) etc..
In the present invention, if not special illustrate, " including " mentioned in this article represents open, or envelope
Enclosed.For example, described " including " can represent and can also include the other elements do not listed, it is also possible to only including the unit for listing
Part.
The catalyst of the present invention has excellent catalysis activity and splendid mechanical strength, is highly suitable for fluidized-bed reaction
Alkene is prepared by methanol in system.In one embodiment, when using the present invention catalyst enter in a fluidized bed reactor
When the reaction of row methanol-to-olefins, in product, the selectivity of propylene is higher than 40%, more preferably higher than 45%.
Active component in the catalyst of the present invention is ZSM-5 molecular sieve, and this is that a kind of molecular sieve well known in the art is urged
Agent material, directly commercially can buy, it is also possible to synthesize according to literature method.Used in following examples of the present invention
The silica alumina ratio of ZSM-5 molecular sieve is 20-400, preferably 250-400.
For prepare catalyst of the present invention host material be Kaolin, calcined kaolin, kieselguhr, boehmite,
One or more in montmorillonite, with the particle diameter less than 2 microns.By using the host material, raising can be played and urged
The effect of agent intensity, wearability.The host material in roasting process it may happen that a certain degree of dehydration and/or point
Solution, such as boehmite in roasting process are understood dehydration and ultimately form aluminium oxide, it is also possible to which some host material is not
Generation dehydration and/or decomposition.In the present invention, all these components included in product catalyst are referred to as " being derived from described
The component of host material ".
Component from the binding agent of the catalyst of the present invention comprising 10-45 weight %, the component is by binding agent
The remaining component after spray drying and roasting is carried out.The binding agent can improve whole slurry system in slurry stage
Uniformity and fluid property, while being also beneficial to improve the overall mechanical strength of final obtained catalyst, significantly improve which resistance to
Mill property.According to specific needs, the composition of binding agent can be controlled by the species and content of regulation binding agent.For this
One or more in following material of bright precursor:Alkaline silica sol, acidic silicasol, Alumina gel, aluminum phosphate etc..Alkali
Property Ludox represent colloid that silica dioxide granule is formed in water, the mean diameter of the silica dioxide granule is that 8-20 is micro-
Rice, its pH scope are 9-10, and the molecular formula of silicon dioxide contained therein can be denoted as SiO2·nH2O, with the gross weight of the Ludox
Count on the basis of amount, calculate in the form of an oxide, wherein the silicon dioxide comprising 15-40 weight %, 0.2-0.4 weight %
Na2O, and the water of surplus.The viscosity of the alkaline silica sol(25℃)For 2-2.5MPaS, density(25℃)For 1.1-1.3
Gram per centimeter3.Acidic silicasol is also called hydrosol of silicic acid, is that polymeric silica microgranule is dispersed in water the acidity to be formed
Colloid, its pH value are 2-4, are counted, are calculated in the form of an oxide, wherein including on the basis of the gross weight of the acidic silicasol
The silicon dioxide of 30-31 weight %, less than the Na of 0.006 weight %2O, and the water of surplus.The viscosity of the acidic silicasol
(25℃)Less than 6MPaS, density(25℃)For 1.19-1.21 gram per centimeters3, the mean diameter of silica dioxide granule receives for 5-20
Rice, under normal temperature condition can stably keep three months and not form any precipitation.Alumina gel is alumina particle shape in water
Into colloid, wherein solid concentration is 10-40 weight %, and pH value is 1-3, and the mean diameter of alumina particle is 10-50 nanometers,
Wherein the chemical formula of alumina particle can write Al2O3·nH2O。
Method for preparing catalyst of the present invention includes mixing ZSM-5 molecular sieve, host material, binding agent and water
Get up, make aqueous slurry, then the serosity is spray-dried and roasting.On the basis of the gross weight of the aqueous slurry
Meter, wherein the total content of component in addition to water is 20-50 weight %.
In a preferred embodiment of the present invention, it is also contemplated that pore creating material, institute are added in the aqueous slurry
It is can be burned out during roasting to state pore creating material, so as to leave the material in the hole of required size in the catalyst.Pore-creating
Agent is mainly used in giving catalyst pore-creating, increases the contact area of catalyst and material, it is possible to use pore creating material well known in the art
Material, such as starch, graphite etc., but more preferably use sesbania powder, polyvinyl alcohol, methylcellulose.In order to avoid affecting to urge
The catalytic performance of agent, and in order to prevent pore creating material be burned out in roasting process, the consumption of the pore creating material is less.With
Count on the basis of the gross weight of the component in the serosity in addition to water, the content of the pore creating material is about 0.01-1 weight %.
In addition, in order to promote full and uniform dispersion of the various raw materials in aqueous slurry, can also add wherein few
Perhaps dispersant.Can use any dispersant material well known in the art, preferred n-octyl alcohol, ammonium hydrogen carbonate, carbonic acid diammonium hydrogen,
These dispersants also can decompose in roasting process completely and be removed.With the gross weight of the component in the serosity in addition to water
Count on the basis of amount, the content of the dispersant is about 0.01-1 weight %.
Above-mentioned aqueous slurry is spray-dried by spray dryer in the present invention.In spray-drying process,
Interior is being dried by slurry spraying first, itself and hot air is then being made so that the moisture in serosity droplet gasifies rapidly, from
And obtain the dry products with general uniform granularity and shape.Present invention preferably uses atomizer exsiccator or pressure type
Spray dryer is spray-dried.The difference of both spray dryers is that the mode being atomized to serosity is different.
In atomizer exsiccator, serosity is transported in the centrifugal turntable for being rotated in nebulizer at a high speed, serosity is quickly thrown away and
It is atomized which.Serosity is spurted into using high-pressure pump and is dried interior by press spray exsiccator so as to form vaporific.
Embodiment
The present invention is conducted further description with reference to embodiment.In the examples below, the ZSM-5 catalysis for using
The silica alumina ratio of agent is 20-400, preferred 250-400;Alkaline silica sol is the Ludox that solid concentration is 30 weight %, and pH value is
9, solid particle mean diameter is 14nm;Acidic silicasol is the Ludox that solid concentration is 30 weight %, and pH value is 2, solid
Mean particle size is 14nm;Alumina gel is the Alumina gel that solid concentration is 30 weight %, and pH value is 2, the average grain of solid particle
Footpath is 20nm;Polyvinyl alcohol is buied from the market, and its molecular weight is 16000-20000;Kaolin, boehmite, sesbania powder,
N-octyl alcohol, calcined kaolin, kieselguhr, ammonium hydrogen carbonate, montmorillonite, bicarbonate diammonium and methanol are buied from commercial source, not
Jing is further purified process and directly uses.
The catalyst of the present invention is prepared in below example 1-5.
Embodiment 1
Add 600g ZSM-5 catalyst fineses (silica alumina ratio is 250), 1200g alkalescence silicon in the stainless steel cauldron of 5L
Colloidal sol, 600g Kaolin, 400g boehmites, 2g sesbania powders, 1g n-octyl alcohols, 4000g deionized waters, stir system
Aqueous slurry is obtained, is spray-dried using atomizer exsiccator, the inlet temperature of the atomizer exsiccator is
300 DEG C, outlet temperature is 180 DEG C, and the charging rate of serosity is 100ml/min, is produced in the middle of the pellet type catalyst of gained of spraying
Thing roasting 2h under conditions of 650 DEG C, air atmosphere in Muffle furnace, obtains catalyst 1#.
Embodiment 2
Add 800g ZSM-5 catalyst fineses (silica alumina ratio is 300), 750g acidity silicon in the stainless steel cauldron of 5L
Colloidal sol, 1200g calcined kaolins, 900g boehmites, 4000g deionized waters, sesbania powder 10g, n-octyl alcohol 35g are fully stirred
Uniformly prepared aqueous slurry is mixed, it is spray-dried using atomizer exsiccator, the atomizer exsiccator enters
Mouthful temperature is 300 DEG C, and outlet temperature is 180 DEG C, and the charging rate of serosity is 250ml/min, the particulate catalytic of gained of spraying
Agent intermediate product roasting 4h under conditions of 600 DEG C, air atmosphere in Muffle furnace, obtains catalyst 2#.
Embodiment 3
In the stainless steel cauldron of 5L add 700g ZSM-5 catalyst fineses (silica alumina ratio is 350), 900g Alumina gels,
100g acidic silicasols, 1400g kieselguhr, 30g sesbania powders, 10g n-octyl alcohols, 5000g deionized waters, stir prepared
Aqueous slurry, is spray-dried using press spray exsiccator, and the inlet temperature of the press spray exsiccator is 250
DEG C, outlet temperature is 180 DEG C, and the charging rate of serosity is 275ml/min, and the pellet type catalyst intermediate product of gained of spraying exists
In Muffle furnace under conditions of 500 DEG C, air atmosphere roasting 6h, obtain catalyst 3#.
Embodiment 4
Add 3000g ZSM-5 catalyst fineses (silica alumina ratio is 400), 600g alkalescence silicon in the stainless steel cauldron of 5L
Colloidal sol, 1400g Kaolin, 600g boehmites, 10g polyvinyl alcohol, 10g ammonium hydrogen carbonate, 5000g deionized waters are fully stirred
Uniformly prepared aqueous slurry is mixed, it is spray-dried using atomizer exsiccator, the atomizer exsiccator enters
Mouthful temperature is 300 DEG C, and outlet temperature is 150 DEG C, and the charging rate of the aqueous slurry is 500ml/min, spraying gained
Granular catalyst intermediate product roasting 6h under conditions of 550 DEG C, air atmosphere in Muffle furnace, obtains catalyst 4#.
Embodiment 5
Add 900g ZSM-5 catalyst fineses (silica alumina ratio is 300), 1600g silicon in the stainless steel cauldron of 5L molten
Glue, 800g montmorillonites, 5g sesbania powders, 5g bicarbonate diammonium, 12000g deionized waters, stir prepared aqueous slurry,
It is spray-dried using atomizer exsiccator, the inlet temperature of the atomizer exsiccator is 300 DEG C, outlet temperature
Spend for 200 DEG C, the charging rate of the aqueous slurry is 250ml/min, and the pellet type catalyst intermediate product of gained of spraying exists
In Muffle furnace under conditions of 600 DEG C, air atmosphere roasting 4h, obtain catalyst 5#.
Technique using prior art in following comparative example prepares the catalyst for control experiment.
Comparative example
Take ZSM-5 molecular sieve original powder 1000g(SiO2/Al2O3=200), in the lanthanum nitrate hexahydrate that La concentration is 3 weight %
The dipping of La in 1500g, is carried out at room temperature, after room temperature immersion 24h, is warming up to boiling, while stirring, after into after thick,
120 DEG C of drying, then in 600 times roasting 3h, La/ZSM-5 is obtained, utilize and operate to La/ZSM-5 molecular sieves with dipping La identicals
Carry out impregnating Mg process, Mg loadings are 3.2%, weigh Kaolin 3567g, deionized water 6000g that contents on dry basis is 84%,
Mix with above-mentioned Mg-La/ZSM-5 molecular sieves, stir 30min, colloid mill grinding 30min, spray shaping control spray dryer
Inlet temperature 400, outlet temperature 200, inject pressure 2.0MPa.The catalyst microspheres of molding are used after cooling in 600 roasting 3h
0.1mol/L hydrochloric acid is swapped, liquid volume(ml)Ratio with catalyst solid (g) is 10ml/g, and exchange temperature is 90,
1h, exchanges 2 times every time, is washed with deionized to picking without chloride ion, and 110 drying, 600 roastings more than 2 hours obtain PLa/
HZSM-5 microspherical catalysts, 10gPLa/HZSM-5 microspherical catalysts are loaded in fluidized-bed reactor, carry out silane in 500
Change, tetraethyl orthosilicate is dissolved in methanol, its weight content is 10%, reaction 1 in reactor is passed through with the speed of 30ml/h little
When, after Silanization reaction terminates, air is passed through in 600 DEG C of roastings more than 2 hours, to remove the carbon deposit of catalyst surface, is obtained
0# catalyst.
Embodiment 6
The above-mentioned catalyst 1#-5# of 150g and 0# catalyst are weighed respectively, load diameter 50mm, high 110 centimetres of fluidisation
In bed, fed using the methanol aqueous solution that volumetric concentration is 50%, 460-500 DEG C of temperature of reactor, the mass space velocity of methanol is
2h-1, reaction pressure 0.1MPa carries out reacting the composition of obtained product using these catalyst using gas chromatographic detection.Survey
Methanol conversion 100% is obtained, concrete products distribution when 8 hours after starting to react is shown in Table 1.
Products distribution of 1 catalyst of table in methanol to olefins reaction(Mass percent)
As can be seen from Table 1, compared with existing catalyst, there is the catalyst of the present invention substantially suitable propylene to select
Property, the synthesis step of catalyst of the present invention is more simply too much than existing process in addition, can significantly simplify production technology, reduces into
This.
Embodiment 7
In order to test the life-span of catalyst of the present invention, weigh 150 grams of above-mentioned catalyst 1# and load diameter 50mm, high 110cm
Fluid bed in, compare 1 using alcohol water quality:1 methanol aqueous solution charging, 460-500 DEG C of temperature of reactor, methanol quality air speed
1h-1, reaction pressure 0.1MPa, using gas chromatographic detection using product obtained in these catalyst reactions composition.Measure first
To the composition of product, alcohol conversion 100%, constantly detects that concrete products distribution is shown in Table 2 in the course of reaction of 200h.
Products distribution of the 1# catalyst of 2 present invention of table in methanol to olefins reaction(Mass percent)
Time/h | CH4 | C2H4 | C3H6 | C4 | C5 |
10 | 0.48 | 9.44 | 46.79 | 23.72 | 13.32 |
50 | 0.41 | 8.66 | 46.95 | 24.16 | 12.76 |
100 | 0.58 | 8.62 | 49.16 | 24.89 | 12.80 |
150 | 0.84 | 9.66 | 46.54 | 23.14 | 12.43 |
200 | 1.20 | 9.14 | 46.01 | 23.51 | 12.30 |
Can be seen by upper table 2, the catalyst of the present invention is used afterwards still can be effectively more than 200 hours
Its catalysis activity and selectivity are kept, gratifying service life is shown.
Embodiment 8
Abrasion index test is carried out to 3# and 0# catalyst using vertical abrasion index tester, standard is adopted for ASTM-
D5757-00, is control sample using Chang Ling FCC poising agents, and Chang Ling FCC poising agents abrasion index is 2.5%, 3# catalyst abrasions
Index is 1.7%, and 0# catalyst abrasions index is 5.8%.As can be seen here, compared with the catalyst of prior art, the present invention
Catalyst there is the wear resistance that significantly improves.
Claims (10)
1. a kind of method for preparing catalyst, the catalyst is the catalysis for alkene is prepared by methanol in fluid bed
Agent, the method comprising the steps of:
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, is configured to aqueous slurry, with the aqueous slurry
Gross weight on the basis of count, wherein the total content of component in addition to water is 20-50 weight %, with the serosity except water
On the basis of the gross weight of component in addition count, in the serosity content of ZSM-5 molecular sieve be 20-55 weight %, the ZSM-5
The silica alumina ratio of molecular sieve is Si/Al=20-400, is counted, institute on the basis of the gross weight of the component in the serosity in addition to water
The content for stating host material described in serosity is 20-59 weight %, and the particle diameter of the host material is less than 2 microns, selected from following
One or more in material:Kaolin, calcined kaolin, kieselguhr, boehmite, montmorillonite, to remove in the serosity
Count on the basis of the gross weight of the component beyond water, the content of binding agent described in the serosity is 20-50 weight %, it is described viscous
Knot agent is acidic silicasol and Alumina gel, and also comprising dispersant, the dispersant is n-octyl alcohol to the serosity, with the serosity
Count on the basis of the gross weight of component in addition to water, in the serosity, the content of dispersant is 0.01-1 weight %;
(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained;
(3) roasting is carried out to graininess intermediate product obtained in step (2), be obtained for alkene being prepared by methanol in fluid bed
The catalyst of hydrocarbon.
2. the method for claim 1, it is characterised in that the gross weight with the component in the serosity in addition to water is
Benchmark meter, in the serosity, the content of ZSM-5 molecular sieve is 20-55 weight %, and the silica alumina ratio of the ZSM-5 molecular sieve is Si/
Al=200-400.
3. the method for claim 1, it is characterised in that the serosity also includes pore creating material.
4. method as claimed in claim 3, it is characterised in that one or more in following material of the pore creating material:
Sesbania powder, polyvinyl alcohol, methylcellulose, are counted on the basis of the gross weight of the component in the serosity in addition to water, described
The content of pore creating material described in serosity is 0.01-1 weight %.
5. the method as any one of claim 1-4, it is characterised in that in the step (2), using atomizer
Exsiccator or press spray exsiccator are spray-dried, and the inlet temperature of spray dryer is 250-300 DEG C, outlet temperature
For 150-200 DEG C, it is 100-500ml/min that serosity is input into the feed rate of the spray dryer.
6. the method as any one of claim 1-4, it is characterised in that in the step (3), at 400-600 DEG C
At a temperature of the roasting of 3-6 hours is carried out to the graininess intermediate product.
7. the method as any one of claim 1-4, it is characterised in that in the step (3), in 550 DEG C of temperature
The roasting of 4 hours is carried out under degree to the graininess intermediate product.
8. the catalyst that prepared by a kind of method by any one of claim 1-4, with the gross weight of the catalyst
On the basis of count, the catalyst comprising 25-60 weight % ZSM-5 molecular sieve, 20-50 weight % from the host material
Component and 10-45 weight % the component from the binding agent, the particle diameter of the catalyst is 50-110 microns.
9. catalyst as claimed in claim 8, it is characterised in that ZSM-5 molecule of the catalyst comprising 25-40 weight %
Sieve, the component from the binding agent of the component and 25-40 weight % from the host material of 30-45 weight %,
The particle diameter of the catalyst is 50-110 microns.
10. a kind of method for preparing alkene by methanol, the method include, is being sufficient so that methanol and is converted into the reaction condition of alkene
Under, it is in a fluidized bed reactor so that the aqueous solution of methanol or methanol is contacted with the catalyst described in claim 8, described anti-
The condition is answered to be:Methanol quality air speed 0.5-5h-1, reaction temperature 430-550 DEG C, reaction pressure 0-1MPa.
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CN108262069B (en) * | 2017-01-04 | 2021-06-22 | 中国石油化工股份有限公司 | Method for producing a fluidized bed catalyst, catalyst produced and use thereof |
CN109721447A (en) * | 2017-10-27 | 2019-05-07 | 上海碧科清洁能源技术有限公司 | A method of olefin product is prepared using ciculation fluidized bed reaction technique |
CN108404970B (en) * | 2018-03-05 | 2020-02-18 | 中国科学院山西煤炭化学研究所 | Apple-shaped hollow molecular sieve microsphere and preparation method and application thereof |
CN109225235B (en) * | 2018-10-10 | 2021-07-20 | 上海兖矿能源科技研发有限公司 | High-efficiency wear-resistant iron-based catalyst for Fischer-Tropsch synthesis in slurry bed and preparation method and application thereof |
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