CN103962169A - Catalyst for methanol-to-olefin in fluidized bed and preparation method thereof - Google Patents
Catalyst for methanol-to-olefin in fluidized bed and preparation method thereof Download PDFInfo
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- CN103962169A CN103962169A CN201310040880.0A CN201310040880A CN103962169A CN 103962169 A CN103962169 A CN 103962169A CN 201310040880 A CN201310040880 A CN 201310040880A CN 103962169 A CN103962169 A CN 103962169A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000002002 slurry Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- 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 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007921 spray Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 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 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000001694 spray drying Methods 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- -1 bicarbonate diamines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 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
- 230000005855 radiation Effects 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000000192 social effect Effects 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
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- 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 catalyst preparation method. The method comprises the steps of: (1) mixing a ZSM-5 molecular sieve, a matrix material, a binder and water to prepare an aqueous slurry, with the total content of the ingredients except water accounting for 20-50% of the total weight of the aqueous slurry; (2) conducting spray drying on the slurry prepared by step (1) to obtain a granular intermediate product; and (3) roasting the granular intermediate product prepared by step (2) to obtain the catalyst for preparation of olefin from methanol in a fluidized bed. The invention also provides the catalyst prepared by the method and the method of using the catalyst to prepare olefin from methanol in a fluidized bed.
Description
Technical field
The present invention relates generally to catalytic field, more particularly, the present invention relates to a kind of Catalysts and its preparation method for alkene by Methanol for fluidized-bed reactor.
Background technology
Ethene, propylene, butadiene are important industrial chemicals, generally to obtain from naphtha pyrolysis and steam cracking, another main source of propylene is ethene propylene simultaneously and refinery's by-product propylene, but these modes of production are difficult to meet the growing demand to propylene of China, China from resource distribution many coals and few oil, methanol device production capacity surplus, the technology of Devoting Major Efforts To Developing methanol-to-olefins has very important economy and social effect.In the technique of the various methanol-to-olefins of having reported, taking ZSM-5 molecular sieve as catalyst, use methyl alcohol to pay attention to greatly for the MTP technology of the synthetic alkene of raw material has been subject to people at present.
LURGI of Germany has developed methanol-to-olefins bed technology (WO2004/018089), utilize ZSM-5 molecular sieve catalyst and the fixed bed reactors of South Chemical Company to carry out methanol to olefins reaction, Propylene Selectivity is 35～40%, CN102531823A, CN101172918B, CN101279280B, CN101402049A, CN102211971A has also announced respectively and has used fixed bed reactors to carry out technique and the method for preparing catalyst of preparing propylene from methanol, mainly taking ZSM-5 molecular sieve as active component, it is carried out to various modifications, thereby the one way that improves propylene is selective.But the reaction of methanol-to-olefins is strong exothermal reaction, in the situation that using fixed bed reactors, at laboratory stage, because loaded catalyst is fewer, and water/alcohol is than high, can remove unnecessary heat by the water in reaction system.And after carrying out industry and amplifying, the poor feature of fixed bed reactors heat transfer property just highlights at once, because heat radiation is bad, in fixed bed reactors, can exist a lot of overheated regions, catalyst to be easy to due to the too high and coking and deactivation of bed temperature.In order to address this problem, people have taked some compromise additional steps.For example, at present in the strange MTP technology in industrialized Shandong, methanol feedstock first, by dimethyl ether reactor, is converted into methanol/dimethyl ether gaseous mixture therein, and then enters MTP fixed bed and react.In addition, in order to promote to conduct heat, in fixed bed reactors, reaction gas is evenly divided into six sections and enters into multi-layer fixed-bed reactor.Above measure has improved process complexity and operation cost greatly.In addition, even in the situation that taking these measures, the heat transfer property of fixed bed reactors still cannot reach desirable level completely, and the yield of propylene is difficult to the level that reaches desirable.
In order to solve the poor problem of fixed bed reactors conductivity of heat, fluid bed is a kind of very desirable selection, and the heat transfer property of fluidized-bed reaction system is significantly better than fixed bed.But, shape, granule strength and the wearability of fluidized-bed reactor to catalyst requires higher, the intensity of the fixed bde catalyst described in above bibliography and wearability are all poor, and its shape is difficult to carry out fluidisation in fluid bed, therefore developing a kind of cheapness, high catalytic activity and have high strength and the catalyst of high-wearing feature, is the bottleneck of current methanol-to-olefins fluidized-bed process exploitation.
Studies have reported that a kind of technology of preparing being used in fluid bed by methanol-to-olefins catalyst, this utilization ZSM-5 molecular sieve is active component, add the components such as rare-earth modifier, alkaline modifier to improve the activity of molecular sieve, apply the methanol-to-olefins fluidized-bed reaction that this catalyst carries out and reach the highest 55% Propylene Selectivity, but this kind of catalyst preparation process complexity, cost is higher, and strength ratio is lower, still can not be satisfactory.Therefore, those skilled in the art, in the urgent need to developing a kind of cheap catalyst with high catalytic activity, high strength, high-wearing feature, are used in fluidized-bed reaction system, carrying out by Methanol the reaction for alkene.
Summary of the invention
In order to address the above problem, the present invention uses ZSM-5 molecular sieve for active component, add therein host material, binding agent, pore creating material and dispersant, prepare the fluidized-bed reaction catalyst for methanol-to-olefins by spray-dired forming method, this kind catalyst preparation process is simple, cost is low, compare with fixed bed MTP technology, do not need to use dimethyl ether pre-reactor, can use the methanol aqueous solution of low water alcohol ratio or methyl alcohol directly to enter fluidized-bed reactor as raw material and react.Catalyst of the present invention has splendid intensity and wearability, reacts after 200h in fluid bed, and propylene still has very high yield.
Of the present invention aspect first in, a kind of method that is used for Kaolinite Preparation of Catalyst is provided, described catalyst be at fluid bed by Methanol the catalyst for alkene, said method comprising the steps of:
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, be mixed with aqueous slurry, taking the gross weight of this aqueous slurry as benchmark, wherein the total content of the component except water is 20-50 % by weight;
(2) slurries that step (1) made are sprayed dry, make graininess intermediate product;
(3) graininess intermediate product step (2) being made carries out roasting, make at fluid bed by Methanol the catalyst for alkene.
In an embodiment of the invention, taking the gross weight of the component except water in described slurries as benchmark, in described slurries, the content of ZSM-5 molecular sieve is 20-55 % by weight, and the silica alumina ratio of described ZSM-5 molecular sieve is Si/Al=20-400, preferably 200-400.
In yet another embodiment of the present invention, taking the gross weight of the component except water in described slurries as benchmark, the content of host material described in described slurries is 20-59 % by weight, the particle diameter of described host material is less than 2 microns, is selected from one or more in following material: kaolin, calcined kaolin, diatomite, boehmite, montmorillonite.
In yet another embodiment of the present invention, taking the gross weight of the component except water in described slurries as benchmark, the content of binding agent described in described slurries is 20-50 % by weight, and described binding agent is selected from one or more in following material: alkaline silica sol, acidic silicasol, aluminium colloidal sol, aluminum phosphate.
In yet another embodiment of the present invention, described slurries also comprise pore creating material.Preferably, described pore creating material is selected from one or more in following material: sesbania powder, polyvinyl alcohol, methylcellulose, taking the gross weight of the component except water in described slurries as benchmark, the content of pore creating material described in described slurries is 0.01-1 % by weight.Another preferred embodiment in, described slurries also comprise dispersant, described dispersant is selected from one or more in following material: n-octyl alcohol, carbonic hydroammonium, bicarbonate two ammoniums, taking the gross weight of the component except water in described slurries as benchmark, in described slurries, the content of dispersant is 0.01-1 % by weight.
In yet another embodiment of the present invention, in described step (2), use centrifugal spray dryer or press spray drier to spray dry, the inlet temperature of spray dryer is 250-300 DEG C, outlet temperature is 150-200 DEG C, and the feed rate that slurries are inputted described spray dryer is 100-500ml/min; In described step (3), 400-600 DEG C, preferably at the temperature of 550 DEG C, described graininess intermediate product is carried out to 3-6 hour, the preferably roasting of 4 hours.
Another aspect of the present invention provides a kind of catalyst of preparing by method of the present invention, taking the gross weight of described catalyst as benchmark, described catalyst comprises 25-60 % by weight, preferably ZSM-5 molecular sieve, 20-50 % by weight, the preferably component that is derived from described host material of 30-45 % by weight and 10-45 % by weight, the preferred component that is derived from described binding agent of 25-40 % by weight of 25-40 % by weight, and the particle diameter of this catalyst is 50-110 micron.
The 3rd aspect of the present invention provide a kind of by Methanol the method for alkene, the method comprises, be under the reaction condition of alkene being enough to make methanol conversion, in fluidized-bed reactor, the aqueous solution of methyl alcohol or methyl alcohol is contacted with the catalyst of preparing by method of the present invention, and described reaction condition is: methanol quality air speed 0.5-5h
-1, reaction temperature 430-550 DEG C, reaction pressure 0-1MPa.
Detailed description of the invention
" scope " disclosed herein is with the form of lower limit and the upper limit.Can be respectively one or more lower limits, and one or more upper limit.Given range limits by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can limit by this way comprise with capable of being combined, and any lower limit can be combined to form a scope with any upper limit.For example, list the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110 and 80-120 also expects.In addition, if the minimum zone value of listing 1 and 2, and if listed maximum magnitude value 3,4 and 5, scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless there are other explanations, number range " a-b " represents that the breviary that a closes to the arbitrary real array between b represents, wherein a and b are real numbers.For example number range " 0-5 " represents all to have listed the whole real numbers between " 0-5 " herein, and " 0-5 " just the breviary of these combinations of values represents.
If do not particularly not pointed out, this description term " two kinds " used refers to " at least two kinds ".
In the present invention, if not special explanation, all embodiments mentioned in this article and preferred embodiment can be combined to form new technical scheme mutually.
In the present invention, if not special explanation, all technical characterictics mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the present invention, if not special explanation mentioned in this article can sequentially be carried out in steps, also can carry out at random, but preferably in sequence.For example, described method comprises step (a) and (b), represents that described method can comprise in sequence step (a) and (b), also can comprise in sequence step (b) and (a).For example, describedly mention described method and also can comprise step (c), represent that step (c) can random order join described method, for example, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) be can comprise, step (c), (a) and (b) etc. also can be comprised.
In the present invention, if not special explanation, " comprising " mentioned in this article represents open, can be also closed.For example, described " comprising " can represent to comprise other elements of not listing, also can only comprise the element of listing.
Catalyst of the present invention has good catalytic activity and splendid mechanical strength, is highly suitable in fluidized-bed reaction system by Methanol for alkene.In one embodiment, when using in catalyst of the present invention carries out the reaction of methanol-to-olefins in fluidized-bed reactor, propylene selectively higher than 40%, more preferably higher than 45% in product.
Active component in catalyst of the present invention is ZSM-5 molecular sieve, and this is a kind of molecular sieve catalytic agent material well known in the art, can directly on market, buy, also can be synthetic according to literature method.The silica alumina ratio of the ZSM-5 molecular sieve using in following examples of the present invention is 20-400, is preferably 250-400.
Be one or more in kaolin, calcined kaolin, diatomite, boehmite, montmorillonite for the preparation of the host material of catalyst of the present invention, there is the particle diameter that is less than 2 microns.By using described host material, can play the effect that improves catalyst strength, wearability.May there is dehydration and/or decomposition to a certain degree in described host material, for example boehmite is understood dehydration and finally formed aluminium oxide in roasting process, also may dehydration and/or decomposition not occur some host material in roasting process.In the present invention, all these components that comprise in product catalyst are referred to as to " component that is derived from described host material ".
The component that is derived from described binding agent that catalyst of the present invention comprises 10-45 % by weight, this component is by binding agent remaining component after spray dry and roasting.Described binding agent can improve in slurry stage uniformity and the fluid property of whole slurries system, is also conducive to improve the overall mechanical strength of the catalyst finally making simultaneously, significantly improves its wearability.According to concrete needs, can control by the kind of adjusting binding agent and content the composition of binding agent.Be selected from one or more of following material for precursor of the present invention: alkaline silica sol, acidic silicasol, aluminium colloidal sol, aluminum phosphate etc.Alkaline silica sol represents the colloid that silica dioxide granule forms in water, and the average grain diameter of described silica dioxide granule is 8-20 micron, and its pH scope is 9-10, and wherein silica containing molecular formula can be denoted as SiO
2nH
2o, taking the gross weight of this Ludox as benchmark, calculates with oxide form, wherein comprises the silica of 15-40 % by weight, the Na of 0.2-0.4 % by weight
2o, and the water of surplus.The viscosity (25 DEG C) of described alkaline silica sol is 2-2.5MPaS, and density (25 DEG C) is 1.1-1.3 gram per centimeter
3.Acidic silicasol is called again hydrosol of silicic acid, it is the acidoid that polymeric silica microparticulate forms in water, its pH value is 2-4, taking the gross weight of described acidic silicasol as benchmark, calculate with oxide form, wherein comprise the silica of 30-31 % by weight, be less than the Na of 0.006 % by weight
2o, and the water of surplus.The viscosity (25 DEG C) of described acidic silicasol is less than 6MPaS, and density (25 DEG C) is 1.19-1.21 gram per centimeter
3, the average grain diameter of silica dioxide granule is 5-20 nanometer, can stablize to keep three months and do not form any precipitation under normal temperature condition.Aluminium colloidal sol is the colloid that alumina particle forms in water, and wherein solid concentration is 10-40 % by weight, and pH value is 1-3, and the average grain diameter of alumina particle is 10-50 nanometer, and wherein the chemical formula of alumina particle can be write Al
2o
3nH
2o.
The method that is used for preparing catalyst of the present invention comprises ZSM-5 molecular sieve, host material, binding agent, He Shui is mixed, and makes aqueous slurry, then to these slurries spray dry and roasting.Taking the gross weight of described aqueous slurry as benchmark, wherein the total content of the component except water is 20-50 % by weight.
In a preferred embodiment of the present invention, it is also conceivable that in described aqueous slurry and add pore creating material, described pore creating material can be burnouted in the process of roasting, thereby in catalyst, leaves the material in the hole of required size.Pore creating material is mainly used in to catalyst pore-creating, increases the contact area of catalyst and material, can use pore former material well known in the art, such as starch, graphite etc., but more preferably use sesbania powder, polyvinyl alcohol, methylcellulose.For fear of the catalytic performance that affects catalyst, and in order to prevent that pore creating material from cannot be burnouted in roasting process, the consumption of this pore creating material is less.Taking the gross weight of the component except water in described slurries as benchmark, the content of described pore creating material is about 0.01-1 % by weight.
In addition, in order to promote the full and uniform dispersion of various raw materials in aqueous slurry, can also add therein the dispersant of a little.Can use any dispersant material well known in the art, preferably n-octyl alcohol, carbonic hydroammonium, bicarbonate diamines, these dispersants also can decompose completely and be removed in roasting process.Taking the gross weight of the component except water in described slurries as benchmark, the content of described dispersant is about 0.01-1 % by weight.
Above-mentioned aqueous slurry is sprayed dry by spray dryer in the present invention.In spray-drying process, first in hothouse by slurry spraying, then make it contact with hot-air, the moisture in slurries droplet is gasified rapidly, thereby obtains having the dry products of uniform particle size and shape substantially.It is dry that the present invention preferably uses centrifugal spray dryer or press spray drier to spray.The difference of these two kinds of spray dryers is slurries to carry out the mode difference of atomization.In centrifugal spray dryer, slurries are transported in the centrifugal turntable of High Rotation Speed in atomizer, slurries are thrown away fast and make its atomization.Press spray drier uses high-pressure pump that slurries are spurted in hothouse, makes its formation vaporific.
Embodiment
Below in conjunction with embodiment, the present invention is conducted further description.In following examples, the silica alumina ratio of the ZSM-5 catalyst of use is 20-400, preferably 250-400; Alkaline silica sol is that solid concentration is the Ludox of 30 % by weight, and pH value is 9, and solid particle average grain diameter is 14nm; Acidic silicasol is that solid concentration is the Ludox of 30 % by weight, and pH value is 2, and solid particle average grain diameter is 14nm; Aluminium colloidal sol is that solid concentration is the aluminium colloidal sol of 30 % by weight, and pH value is 2, and solid particle average grain diameter 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, diatomite, carbonic hydroammonium, montmorillonite, bicarbonate two ammoniums and methyl alcohol are all buied from commercial source, process and directly use without being further purified.
In following embodiment 1-5, prepare catalyst of the present invention.
Embodiment 1
In the stainless steel cauldron of 5L, add 600g ZSM-5 catalyst fines (silica alumina ratio is 250), 1200g alkaline silica sol, 600g kaolin, 400g boehmite, 2g sesbania powder, 1g n-octyl alcohol, 4000g deionized water, stir and make aqueous slurry, use centrifugal spray dryer to spray dry, the inlet temperature of described centrifugal spray dryer is 300 DEG C, outlet temperature is 180 DEG C, the charging rate of slurries is 100ml/min, spraying gained pellet type catalyst intermediate product in Muffle furnace at 650 DEG C, roasting 2h under the condition of air atmosphere, obtain catalyst 1#.
Embodiment 2
In the stainless steel cauldron of 5L, add 800g ZSM-5 catalyst fines (silica alumina ratio is 300), 750g acidic silicasol, 1200g calcined kaolin, 900g boehmite, 4000g deionized water, sesbania powder 10g, n-octyl alcohol 35g, stir and make aqueous slurry, use centrifugal spray dryer to spray dry, the inlet temperature of described centrifugal spray dryer is 300 DEG C, outlet temperature is 180 DEG C, the charging rate of slurries is 250ml/min, spraying gained pellet type catalyst intermediate product in Muffle furnace at 600 DEG C, roasting 4h under the condition of air atmosphere, obtain catalyst 2#.
Embodiment 3
In the stainless steel cauldron of 5L, add 700g ZSM-5 catalyst fines (silica alumina ratio is 350), 900g aluminium colloidal sol, 100g acidic silicasol, 1400g diatomite, 30g sesbania powder, 10g n-octyl alcohol, 5000g deionized water, stir and make aqueous slurry, working pressure formula spray dryer is sprayed dry, the inlet temperature of described press spray drier is 250 DEG C, outlet temperature is 180 DEG C, the charging rate of slurries is 275ml/min, spraying gained pellet type catalyst intermediate product in Muffle furnace at 500 DEG C, roasting 6h under the condition of air atmosphere, obtain catalyst 3#.
Embodiment 4
In the stainless steel cauldron of 5L, add 3000g ZSM-5 catalyst fines (silica alumina ratio is 400), 600g alkaline silica sol, 1400g kaolin, 600g boehmite, 10g polyvinyl alcohol, 10g carbonic hydroammonium, 5000g deionized water, stir and make aqueous slurry, use centrifugal spray dryer to spray dry, the inlet temperature of described centrifugal spray dryer is 300 DEG C, outlet temperature is 150 DEG C, the charging rate of described aqueous slurry is 500ml/min, spraying gained pellet type catalyst intermediate product in Muffle furnace at 550 DEG C, roasting 6h under the condition of air atmosphere, obtain catalyst 4#.
Embodiment 5
In the stainless steel cauldron of 5L, add 900g ZSM-5 catalyst fines (silica alumina ratio is 300), 1600g Ludox, 800g montmorillonite, 5g sesbania powder, 5g bicarbonate two ammoniums, 12000g deionized water, stir and make aqueous slurry, use centrifugal spray dryer to spray dry, the inlet temperature of described centrifugal spray dryer is 300 DEG C, outlet temperature is 200 DEG C, the charging rate of described aqueous slurry is 250ml/min, spraying gained pellet type catalyst intermediate product in Muffle furnace at 600 DEG C, roasting 4h under the condition of air atmosphere, obtain catalyst 5#.
In following comparative example, adopt the technique of prior art for the preparation of the catalyst of control experiment.
Comparative example
Get the former powder 1000g(SiO of ZSM-5 molecular sieve
2/ Al
2o
3=200), be in the lanthanum nitrate hexahydrate 1500g of 3 % by weight in La concentration, at room temperature carry out the dipping of La, after room temperature dipping 24h, be warming up to boiling, stir simultaneously, wait become thick after, 120 DEG C of oven dry, again at 600 times roasting 3h, obtain La/ZSM-5, utilizing the operation identical with dipping La to flood Mg to La/ZSM-5 molecular sieve processes, Mg loading is 3.2%, take contents on dry basis and be 84% kaolin 3567g, deionized water 6000g, mix with above-mentioned Mg-La/ZSM-5 molecular sieve, stir 30min, colloid mill grinds 30min, spray shaping, control the inlet temperature 400 of spray dryer, outlet temperature 200, injection pressure 2.0MPa.The catalyst microspheres of moulding is in 600 roasting 3h, cooling exchange with 0.1mol/L hydrochloric acid afterwards, liquid volume (ml) is 10ml/g with the ratio of catalyst solid (g), exchange temperature is 90, each 1h, exchange 2 times, wash extremely and pick without chlorion by deionized water, 110 dry, 600 roastings are more than 2 hours, obtain PLa/HZSM-5 microspherical catalyst, 10gPLa/HZSM-5 microspherical catalyst is loaded in fluidized-bed reactor, carry out silanization in 500, tetraethyl orthosilicate is dissolved in methyl alcohol, its weight content is 10%, pass in reactor and react 1 hour with the speed of 30ml/h, after Silanization reaction finishes, pass into air in 600 DEG C of roastings more than 2 hours, to remove the carbon deposit of catalyst surface, obtain 0# catalyst.
Embodiment 6
Take respectively the above-mentioned catalyst 1#-5# of 150g and 0# catalyst, pack in diameter 50mm, the fluid bed of high 110 centimetres, use the methanol aqueous solution charging that volumetric concentration is 50%, temperature of reactor 460-500 DEG C, the mass space velocity of methyl alcohol is 2h
-1, reaction pressure 0.1MPa, uses gas chromatographic detection to use these catalyst to react the composition of the product making.Record methanol conversion 100%, the concrete product while starting to react 8 hours afterwards distributes in table 1.
The product distribution (mass percent) of table 1 catalyst in methanol to olefins reaction
As can be seen from Table 1, compared with existing catalyst, catalyst of the present invention has substantially suitable Propylene Selectivity, and the synthesis step of catalyst of the present invention is more simply too much than existing technique in addition, can significantly simplify production technology, reduces costs.
Embodiment 7
In order to test the life-span of catalyst of the present invention, take 150 grams of above-mentioned catalyst 1# and pack in the fluid bed of diameter 50mm, high 110cm, use alcohol water quality than the methanol aqueous solution charging of 1:1, temperature of reactor 460-500 DEG C, methanol quality air speed 1h
-1, reaction pressure 0.1MPa, uses gas chromatographic detection to use the composition of the product that these catalyst reactions make.Record methanol conversion 100%, in the course of reaction of 200h, constantly the composition of product is detected, concrete product distributes in table 2.
The product distribution (mass percent) of table 2 1# catalyst of the present invention in methanol to olefins reaction
| 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 see by upper table 2, catalyst of the present invention still can keep its catalytic activity and selective effectively having used after exceeding 200 hours, shows gratifying service life.
Embodiment 8
Use vertical wearing and tearing index tester to carry out abrasion index test to 3# and 0# catalyst, employing standard is ASTM-D5757-00, use Chang Ling FCC poising agent for contrast sample, Chang Ling FCC poising agent abrasion index is 2.5%, 3# catalyst abrasion index is 1.7%, and 0# catalyst abrasion index is 5.8%.As can be seen here, compared with the catalyst of prior art, catalyst of the present invention has the mar proof significantly improving.
Claims (12)
1. be used for the method for Kaolinite Preparation of Catalyst, described catalyst be at fluid bed by Methanol the catalyst for alkene, said method comprising the steps of:
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, be mixed with aqueous slurry, taking the gross weight of this aqueous slurry as benchmark, wherein the total content of the component except water is 20-50 % by weight;
(2) slurries that step (1) made are sprayed dry, make graininess intermediate product;
(3) graininess intermediate product step (2) being made carries out roasting, make at fluid bed by Methanol the catalyst for alkene.
2. the method for claim 1, it is characterized in that, taking the gross weight of the component except water in described slurries as benchmark, in described slurries, the content of ZSM-5 molecular sieve is 20-55 % by weight, the silica alumina ratio of described ZSM-5 molecular sieve is Si/Al=20-400, preferably 200-400.
3. the method for claim 1, it is characterized in that, taking the gross weight of the component except water in described slurries as benchmark, the content of host material described in described slurries is 20-59 % by weight, the particle diameter of described host material is less than 2 microns, is selected from one or more in following material: kaolin, calcined kaolin, diatomite, boehmite, montmorillonite.
4. the method for claim 1, it is characterized in that, taking the gross weight of the component except water in described slurries as benchmark, the content of binding agent described in described slurries is 20-50 % by weight, and described binding agent is selected from one or more in following material: alkaline silica sol, acidic silicasol, aluminium colloidal sol, aluminum phosphate.
5. the method for claim 1, is characterized in that, described slurries also comprise pore creating material.
6. method as claimed in claim 5, it is characterized in that, described pore creating material is selected from one or more in following material: sesbania powder, polyvinyl alcohol, methylcellulose, taking the gross weight of the component except water in described slurries as benchmark, the content of pore creating material described in described slurries is 0.01-1 % by weight.
7. the method for claim 1, is characterized in that, described slurries also comprise dispersant.
8. method as claimed in claim 7, it is characterized in that, described dispersant is selected from one or more in following material: n-octyl alcohol, carbonic hydroammonium, bicarbonate two ammoniums, taking the gross weight of the component except water in described slurries as benchmark, in described slurries, the content of dispersant is 0.01-1 % by weight.
9. the method as described in any one in claim 1-8, it is characterized in that, in described step (2), use centrifugal spray dryer or press spray drier to spray dry, the inlet temperature of spray dryer is 250-300 DEG C, outlet temperature is 150-200 DEG C, and the feed rate that slurries are inputted described spray dryer is 100-500ml/min.
10. the method as described in any one in claim 1-8, is characterized in that, in described step (3), 400-600 DEG C, preferably at the temperature of 550 DEG C, described graininess intermediate product is carried out to 3-6 hour, the preferably roasting of 4 hours.
11. 1 kinds of catalyst of preparing by the method described in any one in claim 1-8, taking the gross weight of described catalyst as benchmark, the ZSM-5 molecular sieve that described catalyst comprises 25-60 % by weight, preferred 25-40%, the component that is derived from described host material of the preferred 30-45% of 20-50 % by weight and 10-45 % by weight, the preferably component that is derived from described binding agent of 25-40%, the particle diameter of this catalyst is 50-110 micron.
12. 1 kinds by Methanol the method for alkene, the method comprises, is under the reaction condition of alkene, in fluidized-bed reactor being enough to make methanol conversion, the aqueous solution of methyl alcohol or methyl alcohol is contacted with the catalyst described in claim 11, and described reaction condition is: methanol quality air speed 0.5-5h
-1, reaction temperature 430-550 DEG C, reaction pressure 0-1MPa.
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| PCT/CN2014/071737 WO2014117735A1 (en) | 2013-01-31 | 2014-01-29 | Catalyst for preparing olefin from methanol in fluidized bed and preparation method thereof |
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| CN104211086A (en) * | 2014-09-22 | 2014-12-17 | 湖南理工学院 | ZSM-5 zeolite molecular sieve and preparation method thereof |
| CN108262069A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The preparation method of fluid catalyst, the catalyst prepared and its purposes |
| CN108404970A (en) * | 2018-03-05 | 2018-08-17 | 中国科学院山西煤炭化学研究所 | A kind of apple shape hollow molecules sieve microballoon and its preparation method and application |
| CN109225235A (en) * | 2018-10-10 | 2019-01-18 | 上海兖矿能源科技研发有限公司 | High-efficiency abrasion-proof syrup state bed Fischer Tropsch synthesis iron base catalyst and its preparation method and application |
| 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 |
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| CN101274283A (en) * | 2008-04-11 | 2008-10-01 | 中国石油化工股份有限公司 | Method for preparing olefin hydrocarbon catalyst from oxygen-containing compounds |
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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 |
| CN108404970A (en) * | 2018-03-05 | 2018-08-17 | 中国科学院山西煤炭化学研究所 | A kind of apple shape hollow molecules sieve microballoon and its preparation method and application |
| CN109225235A (en) * | 2018-10-10 | 2019-01-18 | 上海兖矿能源科技研发有限公司 | High-efficiency abrasion-proof syrup state bed Fischer Tropsch synthesis iron base catalyst and its preparation method and application |
| 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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