CN110270369A - A kind of methanol, ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene preparation method and applications - Google Patents
A kind of methanol, ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene preparation method and applications Download PDFInfo
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- CN110270369A CN110270369A CN201910525340.9A CN201910525340A CN110270369A CN 110270369 A CN110270369 A CN 110270369A CN 201910525340 A CN201910525340 A CN 201910525340A CN 110270369 A CN110270369 A CN 110270369A
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- Prior art keywords
- ethyl alcohol
- low
- dimethyl ether
- carbon alkene
- microspherical catalyst
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 159
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 33
- 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 29
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- -1 regulator A Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 241000269350 Anura Species 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 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 6
- 238000010008 shearing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 229940001007 aluminium phosphate Drugs 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical group [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical group [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 6
- 150000005218 dimethyl ethers Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 235000019890 Amylum Nutrition 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methanol, ethyl alcohol or dimethyl ethers for the preparation method and applications of microspherical catalyst used in low-carbon alkene.Silicoaluminophosphamolecular molecular sieves SAPO original powder and aluminum saline solution are mixed first, obtain mixed liquor；Deionized water, regulator A, pore creating material B, binder and matrix are added at room temperature to stir evenly；It stirs evenly gained mixed liquor and carries out high speed shear dispersion, obtain suspension；Gained suspension is spray-dried, and microsphere particle is formed；Microsphere particle is roasted, product methanol, ethyl alcohol or dimethyl ether are obtained after roasting for microspherical catalyst used in low-carbon alkene.Method for preparing catalyst provided by the invention, it is simple and easy to do, it is reproducible；Prepared microspherical catalyst has excellent reactivity worth and high mechanical strength.
Description
One, technical field:
The present invention relates to a kind of preparation methods of microspherical catalyst, and in particular to a kind of methanol, ethyl alcohol or dimethyl ether
The preparation method and applications of microspherical catalyst used in standby low-carbon alkene.
Two, background technique:
Ethylene and propylene are important basic chemical industry raw material, mainly for the production of plastics and other chemical products.Generation at present
The steam cracking of the ethylene from petroleum-based feedstock on boundary upper 98%, propylene then mainly with steam cracking production ethylene joint product and
Two kinds of forms of byproduct of catalytic cracking obtain.In recent years, with the sustainable growth of oil demand and the rise of crude oil price,
The technology of exploitation non-conventional oil route production ethylene, propylene, which seems, to be even more important.
Methanol is common bulk chemical, can use coal, natural gas etc. and prepares via synthesis gas, production technology is
Through ripe day by day.Non-oil resource, the reserves such as natural gas are very rich, therefore, from raw material supply diversification and sustainable confession
Should be able to power consider, exploitation more and more paid attention to from preparing low carbon olefin hydrocarbon with methanol.
According to the literature, the volume of fluidized-bed reactor can be reduced, is conducive to for low-carbon alkene using dimethyl ether
Reduce the construction investment of device.Dimethyl ether can be prepared from methanol through dehydration, and technique is also highly stable.
By the development and production practices of many years, the main source of ethyl alcohol has biochemical method and chemical method, and wherein biochemical method is raw
The raw material of producing and ethanol is the compound of plant amylum or carbohydrate, also has report using the research achievement of the ethyl alcohol of cellulose preparation recently
Road.These derive from the ethyl alcohol of crops, open the possibility that a kind of renewable resource is used to produce bulk chemical.
Molecular sieve is the porous material with regular framework structure, in the structure there are many channel of uniform pore diameter and greatly
Cage can only allow the molecule less than its aperture to pass through.Low-carbon alcohols over a molecular sieve occur or dimethyl ether low-carbon alkene is anti-
It should be typical shape selective catalysis process.Different kinds of molecules sieve is used equally for catalysis low-carbon alcohols or dimethyl ether olefine reaction.ZSM-5
Molecular sieve has been reported for the reaction earliest, it has the characteristics that react service life length, but the selectivity of low-carbon alkene is relatively low,
And there are the macromolecular substances such as aromatic hydrocarbons in product.Pore zeolite is demonstrated by higher low-carbon alkene selection in methanol to olefins reaction
Property, but inactivate quickly.U.S. combinating carbide company discloses the conjunction of silicoaluminophosphate Series Molecules sieve in patent US4440871
At method.So far, it is shown in methanol to olefins reaction well by the small pore molecular sieve of representative of SAPO-34 molecular sieve
Catalytic performance, wherein SAPO-34 is best.But compared with ZSM-5, SAPO-34 molecular sieve is in methanol to olefins reaction
Service life is obviously partially short, and catalytic activity will be completely lost in several hours.Therefore, has the characteristics that the fluidized bed of successive reaction regeneration
More it is suitable for the reaction characteristics of SAPO-34 molecular sieve, using micro-spherical catalyst.
For the microspherical catalyst for preparing low carbon olefin hydrocarbon by methanol, the abrasion resistance properties of reactivity worth and catalyst
It is two aspects for needing to pay close attention to.The economy of the direct decision process of the reactivity worth of catalyst.Meanwhile catalyst needs
With good intensity, to prevent during fluidized reaction, catalyst granules generation rupture dusting (between catalyst granules,
Collision between catalyst and device wall causes).The fine powder of generation is difficult recycling, and not only pollutes the environment, can also
Increase production cost.
Uop Inc., the U.S. (China Patent No. 1341584) discloses the preparation for methanol conversion attrition resistant catalyst, urges
Agent includes aluminum phosphate molecular sieve analog, inorganic oxide binder and clay class filler.By the way that the mass fraction of molecular sieve is protected
It holds 40% or lower, that is, reduces the dosage of SAPO-34 molecular sieve, the wear-resistant strength of catalyst can be improved.
US6153552 has studied a kind of method for preparing molecular sieve catalyst, and this method is by molecular sieve and alumina sol
And phosphorus-containing compound mixing, spray-dried and roasting are made.
US6509290 discloses a kind of method for preparing molecular sieve catalyst, contains in the catalyst and fills from fluidized bed
The broken particle for the catalyst set, specific method include mixing molecular sieve, binder and filler, broken catalyst waste material.It is spraying dry
Dry formation microspherical catalyst.The invention thinks that broken particle is free of coke the intensity that can increase catalyst granules.
CN101259427 discloses a kind of method for preparing high abrasion resistance strength molecular sieve fluid bed catalyst, including will divide
Sub- sieve, binder, basis material, catalyst fines, liquid medium are uniformly mixed to form suspension, shearing dispersion, spray drying
Form microspherical catalyst.
Although existing patent is related to the preparation of wear-resistance microspheres catalyst, there is not also pertinent literature report to prepare wear-resisting catalysis
Microspherical catalyst reactivity worth method can be promoted while agent.Development simplicity, effective method prepare high-strength high-performance
Microspherical catalyst has important value and significance.
Three, summary of the invention:
The technical problem to be solved by the present invention is state of development according to prior art, the present invention provides a kind of methanol, second
Alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene preparation method and applications.Utilize technical solution of the present invention system
Standby microspherical catalyst be applied to methanol, ethyl alcohol or dimethyl ether for low-carbon alkene as catalyst when, have excellent anti-
Answer performance and high mechanical strength.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
The present invention provides a kind of methanol, ethyl alcohol or dimethyl ether for the preparation side of microspherical catalyst used in low-carbon alkene
Method, the preparation method comprises the following steps:
A, silicoaluminophosphamolecular molecular sieves SAPO original powder is mixed with aluminum saline solution according to solid-to-liquid ratio 1g:1~2.5mL,
Then 0.5~3h is stirred under the conditions of 20~50 DEG C, obtains mixed liquor；
B, then at room temperature, into the resulting mixed liquor of step a be added deionized water, regulator A, pore creating material B,
Binder and matrix stir evenly after addition；
Mass ratio between the mixed liquor, deionized water, regulator A, pore creating material B, binder and matrix is 4~7:1:
0.03~0.1:0.05~0.2:4~8:1~3；
C, step b is stirred evenly into gained mixed liquor and carries out high speed shear dispersion, until in gained suspension >=80%
Particle scale is less than 8 microns；
D, step c shearing dispersion gained suspension is spray-dried, and forms microsphere particle；
E, step d thus obtained microsphere particle is roasted, maturing temperature is 450~750 DEG C, and calcining time is 5~7h, roasting
Product methanol, ethyl alcohol or dimethyl ether are obtained after burning for microspherical catalyst used in low-carbon alkene.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Silicoaluminophosphamolecular molecular sieves SAPO described in rapid a is SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 and SAPO-47
At least one of.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Aluminium salt described in rapid a is at least one of aluminum nitrate, aluminium chloride and aluminum sulfate；The concentration of the aluminum saline solution be 0.05~
0.3mol/L。
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Regulator A described in rapid b is in lanthanum acetate, cerous acetate, lanthanum nitrate, cerous nitrate, lanthanum sulfate, cerous sulfate, lanthanum chloride and cerium chloride
At least one.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Pore creating material B described in rapid b is polyacrylamide or polyethylene glycol or two kinds of mixture.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Binder described in rapid b is at least one of silica solution, Aluminum sol, aluminium phosphate sol and boehmite.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
Matrix described in rapid b is at least one of kaolin, metakaolin, montmorillonite, carclazyte, silica and aluminium oxide.
According to above-mentioned methanol, ethyl alcohol or dimethyl ether for the preparation method of microspherical catalyst used in low-carbon alkene, step
The solid content of suspension obtained by rapid c is 25~50%.
Additionally, it is provided a kind of microspherical catalyst of above-mentioned preparation is in methanol, ethyl alcohol or dimethyl ether in low-carbon alkene
Using.
Active and effective beneficial effect of the invention:
1, the method for the present invention use first aluminium ion aqueous solution to molecular screen primary powder carry out low temperature pre-treatment, acid aluminium from
Sub- aqueous solution can play the role of abundant activated molecular sieve surface, be conducive to the phase interaction for increasing molecular sieve and matrix binder
Firmly, to significantly increase the intensity of microspherical catalyst.In addition, in the methods of the invention, carrying out aluminium ion solution to molecular sieve
Pre-treatment, while a small amount of regulator A (salt of lanthanum and/or cerium) being added in slurry, it can effectively promote prepared microballoon and urge
Reactivity worth of the agent in methanol, ethyl alcohol or dimethyl ether low-carbon alkene.
2, method for preparing catalyst provided by the invention, it is simple and easy to do, it is reproducible；Prepared microspherical catalyst has
Excellent reactivity worth and high mechanical strength.
Four, specific embodiment:
The present invention is further explained with reference to embodiments, but is not intended to limit the range of technical solution of the present invention protection.
Embodiment 1:
The preparation method of methanol, ethyl alcohol or dimethyl ether of the present invention for microspherical catalyst used in low-carbon alkene, the preparation
The detailed step of method is as follows:
A, 1kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 1.3kg, 0.25mol/L aluminum chloride aqueous solution
It closes, then stirs 1.5h under the conditions of 40 DEG C, obtain mixed liquor；
B, then at room temperature, into the resulting mixed liquor of step a be added 0.5kg deionized water, 50g lanthanum nitrate,
30g Macrogol 600,2.6kg Aluminum sol (solid content 20%), 0.94kg silica solution (solid content 30%), 0.2kg intend thin
Diaspore (solid content 70%) and 1.25kg kaolin (solid content 80%), stir evenly after addition；
C, step b is stirred evenly into gained mixed liquor and carries out high speed shear dispersion, until in gained suspension >=80%
Particle scale is less than 8 microns；
D, step c shearing dispersion gained suspension is dry using press spray, and microsphere particle is made；
E, step d thus obtained microsphere particle is roasted, maturing temperature is 600 DEG C, and calcining time 6h is obtained after roasting
Product methanol, ethyl alcohol or dimethyl ether are for microspherical catalyst used in low-carbon alkene.
Embodiment 2:
The preparation method of methanol, ethyl alcohol or dimethyl ether of the present invention for microspherical catalyst used in low-carbon alkene, the preparation
The detailed step of method is as follows:
A, 1.5kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 2.0kg, 0.10mol/L aluminum sulfate aqueous solution
It closes, then stirs 3h under the conditions of 30 DEG C, obtain mixed liquor；
B, then at room temperature, into the resulting mixed liquor of step a be added 0.5kg deionized water, 30g cerous nitrate,
20g Macrogol 600,2.4kg Aluminum sol (solid content 20%), 1.05kg silica solution (solid content 30%) and 1.4kg are inclined
Kaolin (solid content 80%), stirs evenly after addition；
C, step b is stirred evenly into gained mixed liquor and carries out high speed shear dispersion, until in gained suspension >=80%
Particle scale is less than 8 microns；
D, step c shearing dispersion gained suspension is dry using press spray, and microsphere particle is made；
E, step d thus obtained microsphere particle is roasted, maturing temperature is 750 DEG C, and calcining time 5h is obtained after roasting
Product methanol, ethyl alcohol or dimethyl ether are for microspherical catalyst used in low-carbon alkene.
Embodiment 3:
The preparation method of methanol, ethyl alcohol or dimethyl ether of the present invention for microspherical catalyst used in low-carbon alkene, the preparation
The detailed step of method is as follows:
A, 2kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 3.0kg, 0.2mol/L aluminum nitrate aqueous solution,
Then 1h is stirred under the conditions of 50 DEG C, obtains mixed liquor；
B, then at room temperature, into the resulting mixed liquor of step a be added 0.7kg deionized water, 15g lanthanum nitrate,
15g cerous nitrate, 20g polyacrylamide, 3.4kg aluminium phosphate sol (solid content 20%), 0.25kg boehmite (solid content
70%) with 1.05kg aluminium oxide (solid content 80%), to be stirred evenly after addition；
C, step b is stirred evenly into gained mixed liquor and carries out high speed shear dispersion, until in gained suspension >=80%
Particle scale is less than 8 microns；
D, step c shearing dispersion gained suspension is dry using atomizer, and microsphere particle is made；
E, step d thus obtained microsphere particle is roasted, maturing temperature is 450 DEG C, and calcining time 7h is obtained after roasting
Product methanol, ethyl alcohol or dimethyl ether are for microspherical catalyst used in low-carbon alkene.
Comparative example 1:
A kind of methanol, the preparation method of ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene, the preparation side
Method is substantially the same manner as Example 1, the difference is that:
In step a: 1kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 1.3kg deionized water.
Comparative example 2:
A kind of methanol, the preparation method of ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene, the preparation side
Method is substantially the same manner as Example 1, the difference is that:
In step b: not adding lanthanum nitrate.
Comparative example 3:
A kind of methanol, the preparation method of ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene, the preparation side
Method is substantially the same manner as Example 2, the difference is that:
In step a: 1.5kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 2.0kg deionized water.
Comparative example 4:
A kind of methanol, the preparation method of ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene, the preparation side
Method is substantially the same manner as Example 3, the difference is that:
In step a: 2kg silicoaluminophosphamolecular molecular sieves SAPO-34 original powder is mixed with 3.0kg deionized water.
Embodiment 5:
The microspherical catalyst that embodiment 1-3 and comparative example 1-4 are prepared carries out abrasion test test, and test result is detailed
It is shown in Table 1.Attrition of catalyst measuring method is carried out according to U.S.'s ASTM D5757-95 standard.It can be seen that: use the technology of the present invention
Aluminium ion aqueous solution carries out pretreated catalyst sample to molecular sieve and shows the abrasion index being substantially reduced in scheme.
The abrasion index of 1 embodiment of the present invention of table and comparative example thus obtained microsphere catalyst
| Sample | Abrasion index (%) |
| Embodiment 1 | 0.5 |
| Comparison example 1 | 1.0 |
| Comparison example 2 | 0.5 |
| Embodiment 2 | 0.6 |
| Comparison example 3 | 1.2 |
| Embodiment 3 | 0.8 |
| Comparison example 4 | 1.2 |
Embodiment 6:
Methanol is carried out to microspherical catalyst prepared by examples detailed above using fixed bed reactors and prepares olefine reaction performance
Experimental test: first sieving the microspherical catalyst tabletting of preparation, and 0.5 gram of 20-40 molecules of interest sieve is taken to be packed into quartzy tube reaction
Device；Logical nitrogen temperature activates 1 hour to 500 DEG C, then cools to 450 DEG C of reaction temperature, and reaction pressure is normal pressure, methanol by
40mL/min nitrogen carries charging, and the mass space velocity of methanol is 2.0h-1.With gas chromatographic analysis product.Reaction result is detailed in table
2。
The microspherical catalyst of 2 examples detailed above of table preparation carries out the experimental test result that methanol prepares olefine reaction performance
Indicate: * in above-mentioned table: the reaction service life is defined as the time that methanol conversion is greater than 99.98%.
Embodiment 7:
The examination of ethyl alcohol olefine reaction performance is carried out to microspherical catalyst prepared by examples detailed above using fixed bed reactors
Test examination: first sieving the microspherical catalyst tabletting of preparation, and 0.5 gram of 20-40 molecules of interest sieve is taken to be packed into quartz tube reactor；
Logical nitrogen temperature activates 1 hour to 500 DEG C, then cools to 450 DEG C of reaction temperature, reaction pressure is normal pressure, and ethyl alcohol is by 40mL/
Min nitrogen carries charging, and the mass space velocity of ethyl alcohol is 2.0h-1.With gas chromatographic analysis product.Reaction result, which is detailed in, is shown in Table 3.
The microspherical catalyst of 3 examples detailed above of table preparation carries out the experimental test result that ethyl alcohol prepares olefine reaction performance
Indicate: * in above-mentioned table: the reaction service life is defined as the time that methanol conversion is greater than 99.98%.
Embodiment 8:
Dimethyl ether is carried out for olefine reaction performance to microspherical catalyst prepared by examples detailed above using fixed bed reactors
Experimental test: microspherical catalyst tabletting screening will be prepared first, 0.5 gram of 20-40 molecules of interest sieve is taken to be packed into quartzy tube reaction
Device；Logical nitrogen temperature activates 1 hour to 500 DEG C, then cools to 450 DEG C of reaction temperature, and reaction pressure is normal pressure, dimethyl ether by
40mL/min nitrogen carries charging, and the mass space velocity of dimethyl ether is 2.0h-1.With gas chromatographic analysis product.Reaction result is detailed in
Table 4.
The microspherical catalyst of 4 examples detailed above of table preparation carries out dimethyl ether for the experimental test result of olefine reaction performance
It can be indicated by embodiment 6, embodiment 7 and embodiment 8, the microspherical catalyst prepared using technical solution of the present invention
Sample, using methanol, ethyl alcohol and dimethyl ether for all showing longer catalytic life and higher in the reaction of low-carbon alkene
Ethylene, Propylene Selectivity.
Claims (9)
1. a kind of methanol, ethyl alcohol or dimethyl ether are for the preparation method of microspherical catalyst used in low-carbon alkene, which is characterized in that
The preparation method comprises the following steps:
A, silicoaluminophosphamolecular molecular sieves SAPO original powder is mixed with aluminum saline solution according to solid-to-liquid ratio 1g:1~2.5mL, then
0.5~3h is stirred under the conditions of 20~50 DEG C, obtains mixed liquor；
B, deionized water, regulator A, pore creating material B, bonding then at room temperature, are added into the resulting mixed liquor of step a
Agent and matrix stir evenly after addition；
Mass ratio between the mixed liquor, deionized water, regulator A, pore creating material B, binder and matrix is 4~7:1:0.03
~0.1:0.05~0.2:4~8:1~3；
C, step b is stirred evenly into gained mixed liquor and carries out high speed shear dispersion, until in gained suspension >=80% particle
Scale is less than 8 microns；
D, step c shearing dispersion gained suspension is spray-dried, and forms microsphere particle；
E, step d thus obtained microsphere particle is roasted, maturing temperature is 450~750 DEG C, and calcining time is 5~7h, after roasting
Product methanol, ethyl alcohol or dimethyl ether are obtained for microspherical catalyst used in low-carbon alkene.
2. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: silicoaluminophosphamolecular molecular sieves SAPO described in step a is SAPO-17, SAPO-18, SAPO-34, SAPO-
35, at least one of SAPO-44 and SAPO-47.
3. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: aluminium salt described in step a is at least one of aluminum nitrate, aluminium chloride and aluminum sulfate；The aluminium salt water
The concentration of solution is 0.05~0.3mol/L.
4. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: regulator A described in step b is lanthanum acetate, cerous acetate, lanthanum nitrate, cerous nitrate, lanthanum sulfate, sulfuric acid
At least one of cerium, lanthanum chloride and cerium chloride.
5. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: pore creating material B described in step b is polyacrylamide or polyethylene glycol or two kinds of mixture.
6. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: binder described in step b be silica solution, Aluminum sol, aluminium phosphate sol and boehmite in extremely
Few one kind.
7. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: matrix described in step b is in kaolin, metakaolin, montmorillonite, carclazyte, silica and aluminium oxide
At least one.
8. methanol according to claim 1, ethyl alcohol or dimethyl ether are for the preparation of microspherical catalyst used in low-carbon alkene
Method, it is characterised in that: the solid content of suspension obtained by step c is 25~50%.
9. microspherical catalyst prepared by a kind of claim 1 is in methanol, ethyl alcohol or dimethyl ether for applying in low-carbon alkene.
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