WO2014117740A1 - 一种高c4烯烃选择性的用来由甲醇制烯烃的催化剂及其制备方法 - Google Patents
一种高c4烯烃选择性的用来由甲醇制烯烃的催化剂及其制备方法 Download PDFInfo
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- WO2014117740A1 WO2014117740A1 PCT/CN2014/071747 CN2014071747W WO2014117740A1 WO 2014117740 A1 WO2014117740 A1 WO 2014117740A1 CN 2014071747 W CN2014071747 W CN 2014071747W WO 2014117740 A1 WO2014117740 A1 WO 2014117740A1
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- Prior art keywords
- catalyst
- weight
- methanol
- water
- olefin
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 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 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 239000013067 intermediate product Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims description 30
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 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 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 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
- 239000004372 Polyvinyl alcohol Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000007767 bonding agent Substances 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- URQMEZRQHLCJKR-UHFFFAOYSA-N 3-Methyl-5-propyl-2-cyclohexen-1-one Chemical compound CCCC1CC(C)=CC(=O)C1 URQMEZRQHLCJKR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- -1 Ethylene, propylene, butadiene Chemical class 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
-
- 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
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/28—Phosphorising
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
Definitions
- This invention relates generally to the field of catalysis and, more particularly, to a process for the preparation of a catalyst for the preparation of olefins from methanol for use in a fluidized bed reactor which produces a catalyst having a high C4 olefin selectivity.
- Ethylene, propylene, butadiene are important chemical raw materials, generally obtained from naphtha cracking and steam cracking.
- the main source of propylene is ethylene co-produced propylene and refinery by-product propylene, while the main source of butadiene is obtained by further processing of C4 by-products from ethylene cracking process, but these production methods are difficult to meet the growing domestic Demand for propylene and butadiene. It is highly desirable to develop a process for producing propylene and C4 olefins with high selectivity.
- the methanol-to-olefin fixed bed technology developed by Luqi Company of Germany (WO2004/018089), using the ZSM-5 molecular sieve of Southern Chemical Company as a catalyst, using a fixed-bed reactor for methanol-to-olefin reaction, the propylene selectivity is 35 ⁇ 40. %.
- CN102531823A, CN101 172918B, CN101279280B, CN101402049A, CN10221 1971A respectively disclose a process for preparing methanol to propylene and a catalyst preparation method in a fixed bed reaction system. Specifically, these processes mainly use ZSM-5 molecular sieve as an active component. It is modified to increase the propylene single pass selectivity.
- the methanol to olefin reaction has a higher selectivity to the C4 olefin, then the butene is separated from the C4 olefin product, and subjected to dehydrogenation treatment to produce butadiene. Will receive a very high additional economic benefit.
- the present invention has developed a novel catalyst which
- ZSM-5 molecular sieve is an active component, which is prepared by mixing with a matrix material, a binder, a pore former and a phosphorus source, and is prepared by a spray drying molding method.
- the catalyst of the present invention is C4.
- the selectivity is up to 32% while still maintaining a high propylene selectivity.
- the catalyst of the present invention also has high mechanical strength and wear resistance, and is highly suitable for use in a fluidized bed system.
- a first aspect of the invention provides a process for preparing a catalyst which is a catalyst for the production of olefins from methanol in a fluidized bed, the process comprising the steps of:
- the particulate intermediate obtained in the step (2) is calcined to obtain a catalyst for producing an olefin from methanol in a fluidized bed.
- the ZSM-5 molecular sieve has a silica-alumina ratio of 20-400, preferably 200-400, based on the total weight of components other than water in the aqueous slurry, the ZSM The content of the -5 molecular sieve is 20 to 55% by weight.
- the matrix material is one or more selected from the group consisting of kaolin, calcined kaolin, diatomaceous earth, pseudoboehmite, and montmorillonite, and has a particle diameter of less than 2 ⁇ .
- the content of the matrix material in the aqueous slurry is from 20 to 59% by weight based on the total weight of the components other than water.
- the binder is selected from the group consisting of an alkaline silica sol, an acidic silica sol, an aluminum sol, an aluminum phosphate, an aluminum nitrate, and an alumina, in the aqueous slurry.
- the binder is contained in an amount of 20 to 50% by weight based on the total weight of the components other than water.
- the phosphorus source is selected from the group consisting of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, and the group other than water in the aqueous slurry.
- the phosphorus source is present in an amount of from 0.1 to 5.0% by weight based on the total weight of the fraction.
- the slurry further comprises a pore forming agent, and the pore forming agent is selected from one or more of the group consisting of phthalocyanine powder, polyvinyl alcohol, and methyl cellulose,
- the pore former is contained in an amount of from 0.01 to 1% by weight based on the total weight of the components other than water in the aqueous slurry.
- the spray drying is performed using a centrifugal spray dryer or a pressure spray dryer, and the inlet temperature of the spray dryer is 150-300 ° C, and the outlet temperature is 120.
- the slurry is fed into the spray dryer at a feed rate of 100-500 ml/min.
- the particulate intermediate product in the step (3), is calcined at a temperature of 550 to 650 ° C, preferably 600 V, for 3 to 6 hours, preferably 4 hours.
- a second aspect of the invention relates to a catalyst for the preparation of an olefin from methanol in a fluidized bed, the catalyst being prepared by the process of the invention, the catalyst comprising 25-based on the total weight of the catalyst 60% by weight, preferably 25-40% by weight of ZSM-5 molecular sieve, 0.05-3% by weight of the component derived from the phosphorus source, 20-50% by weight, preferably 30-45% by weight, derived from the substrate
- a third aspect of the invention relates to a process for the preparation of an olefin from methanol, which comprises, in a fluidized bed reactor, an aqueous solution of methanol or methanol in a fluidized bed reactor under reaction conditions sufficient to convert methanol to olefins
- the catalyst prepared by the method of the invention is contacted, and the reaction conditions are: methanol mass space velocity 0.5-5 h - reaction temperature 430-550 ° C, reaction pressure 0-1.0 MPa; selectivity of propylene in the obtained product is higher than 40 %, preferably above 45%, the selectivity of the olefin comprising four carbon atoms is above 25%, preferably above 28%, more preferably above 30%, most preferably up to 32%.
- the C4 product selectivity of the catalyst is significantly improved.
- the wear resistance was not lowered. detailed description
- the "scope” disclosed in this document is in the form of a lower limit and an upper limit. It can be one or more lower limits, and one or more upper limits.
- the given range is defined by selecting a lower limit and an upper limit.
- the selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, that is, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-1 10 are listed for specific parameters, and ranges of 60-1 10 and 80-120 are also expected. In addition, if the minimum range values listed are 1 and 2, and if the maximum range values 3, 4 and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3. 2-4 and 2-5.
- the numerical range "a-b” denotes an abbreviated representation of any real combination between a and b, unless otherwise stated, where a and b are both real numbers.
- the value range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of the combination of these values.
- the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially.
- the method may also include the step (c), indicating that the step (c) may be added to the method in any order, for example, the method may include steps (a), (b), and (c) Steps (a), (c), and (b) may also be included, and steps (c), (a), and (b) may also be included.
- the C4 component or the C4 product means that all components of the reaction product containing four carbon atoms, most of which are C4 olefins, hence the terms "C4 component”, “C4 product” and “C4 olefin” They can be used interchangeably to denote the same components in the product.
- the C4 olefin of the present invention may include 1-butene, 2-butene, 1,3-butadiene, 2-methyl-1-propene or the like. Isomers such as 1-butene, 2-butene and 2-methyl-1-propene may be subjected to subsequent operations such as dehydrogenation or isomerization to prepare a 1,3-butadiene product. Therefore, the catalyst of the present invention can be used to simultaneously obtain two products of high economic value by a single reaction with high selectivity.
- the active component of the catalyst of the present invention is a ZSM-5 molecular sieve, which is a molecular sieve catalyst material well known in the art and which is commercially available or can be synthesized by literature.
- the ZSM-5 molecular sieve used in the following examples of the invention has a silica to alumina ratio of from 20 to 400, preferably from 200 to 400.
- Phosphorus is introduced into the catalyst by using a phosphorus source selected from one or more selected from the group consisting of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, which are subsequently spray dried.
- P 2 O 5 may be formed on the ZSM-5 molecular sieve during the calcination process, or P may enter the molecular sieve skeleton by substituting Si or A1.
- the matrix material used to prepare the catalyst of the present invention is one or more of kaolin, calcined kaolin, diatomaceous earth, pseudoboehmite, montmorillonite, having a particle size of less than 2 microns.
- the matrix material may undergo some degree of water loss and/or decomposition during the calcination process.
- the pseudo-boehmite may lose water during the roasting process and eventually form alumina, and some of the matrix material may not lose water. And / or decomposition.
- all of the components contained in the product catalyst are collectively referred to as "components derived from the matrix material".
- the catalyst of the present invention comprises from 10 to 45% by weight of the component derived from the binder, which is the component remaining after the spray drying and baking by the binder.
- the binder is capable of improving the uniformity and fluid properties of the entire slurry system in the slurry stage, and is also advantageous for improving the overall mechanical strength of the finally produced catalyst and significantly improving its wear resistance.
- the composition of the binder can be controlled by adjusting the type and content of the binder according to specific needs.
- the precursor used in the present invention is selected from one or more of the following materials: an alkaline silica sol, an acidic silica sol, an aluminum sol, aluminum phosphate, aluminum nitrate, aluminum oxide, and the like.
- the alumina may be amorphous alumina.
- Alkaline silica sol means a gel formed by silica particles in water
- the silica particles have an average particle diameter of 8-20 microns and a pH range of 9-10, wherein the molecular formula of the silica contained therein can be referred to as SiO 2 —nH 2 O, based on the total weight of the silica sol. Calculated as an oxide, it comprises 15-40% by weight of silica, 0.2-0.4% by weight of Na 2 O, and the balance of water.
- the alkaline silica sol has a viscosity (25 ° C) of from 2 to 2.5 MPaS and a density (25 ° C) of from 1.1 to 1.3 g/cm 3 .
- Acidic silica sol also known as silicic acid hydrosol, is an acidic colloid formed by dispersing polymeric silica particles in water, having a pH of 2-4, based on the total weight of the acidic silica sol, based on oxides. Formal calculation, which comprises 30-31% by weight of silica, less than 0.006% by weight of Na 2 O, and the balance of water.
- the acidic silica sol has a viscosity (25 ° C) of less than 6 MPaS, a density (25 ° C) of 1.19-1.21 g/cm 3 , and an average particle diameter of the silica particles of 5-20 nm, which is stable under normal temperature conditions. Hold for three months without forming any precipitate.
- the aluminum sol is a colloid formed of alumina particles in water, wherein the solid concentration is 10-40% by weight, the pH is 1-3, and the average particle diameter of the alumina particles is 10-50 nm, wherein the chemical formula of the alumina particles can be written. ⁇ 1 2 ⁇ 3 ⁇ 2 ⁇ .
- the process for preparing the catalyst of the present invention comprises mixing a ZSM-5 molecular sieve, a phosphorus source, a matrix material, a binder, an optional pore former, and water to form an aqueous slurry, which is then spray dried and calcined. .
- the total content of the components other than water is from 20 to 50% by weight based on the total weight of the aqueous slurry.
- the pore former is a material which is capable of being burned out during the calcination to leave pores of a desired size in the catalyst.
- the pore former is mainly used for pore formation of the catalyst, and the contact area between the catalyst and the material is increased.
- a pore former material known in the art such as starch, graphite, etc., may be used, but it is more preferable to use phthalocyanine powder, polyvinyl alcohol, methyl group. Cellulose.
- the amount of the pore former is small.
- the pore former is present in an amount of from about 0.01% to about 1% by weight based on the total weight of the components of the slurry other than water.
- the above aqueous slurry is spray dried by a spray dryer.
- the slurry is first atomized in a drying chamber and then brought into contact with hot air to rapidly vaporize the moisture in the slurry droplets, thereby obtaining a dried product having a substantially uniform particle size and shape.
- the invention preferably employs a centrifugal spray dryer or a pressure spray dryer for spray drying. The difference between the two spray dryers is the way in which the slurry is atomized.
- a centrifugal spray dryer the slurry is transferred to a high-speed rotating centrifugal turntable in the atomizer, and the slurry is quickly taken out to atomize it.
- the pressure spray dryer uses a high pressure pump to spray the slurry into the drying chamber to form a mist.
- the ZSM-5 catalyst has a silica-alumina ratio of 20-400, preferably 250-400;
- the basic silica sol is a silica sol having a solid concentration of 30% by weight, a pH of 9, and an average particle diameter of the solid particles of 14 nm;
- the acidic silica sol is a silica sol having a solid concentration of 30% by weight, a pH of 2, an average particle diameter of the solid particles of 14 nm;
- an aluminum sol being an aluminum sol having a solid concentration of 30% by weight, a pH of 2, and an average particle diameter of the solid particles of 20 nm;
- Vinyl alcohol is commercially available and has a molecular weight of 16,000 to 20,000; kaolin, pseudoboehmite, phthalocyanine powder, 3 ⁇ 4PO 4 , calcined kaolin, diatomaceous earth, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, Mongolia Both decalcification and methanol were purchased
- Tian Jing powder 50g H3PO4, 4000g deionized water, fully stirred to obtain an aqueous slurry, spray-drying the aqueous slurry using a centrifugal spray dryer, the inlet temperature of the centrifugal spray dryer is 300 ° C, the outlet temperature At 180 ° C, the feed rate of the aqueous slurry was 100 ml/min, and the particles obtained by the spraying were calcined in a muffle furnace in an air atmosphere at a temperature of 650 ° C for 2 hours to obtain a catalyst 2 #.
- the aqueous slurry was spray-dried by a centrifugal spray dryer having an inlet temperature of 300 ° C, an outlet temperature of 180 ° C, and a feed rate of the aqueous slurry of 250 ml/min.
- the pellets were calcined in a muffle furnace in an air atmosphere at a temperature of 600 ° C for 4 hours to obtain a catalyst 3 #.
- Example 1 Add 12000 g of water to a 5 L stainless steel autoclave, add 900 g of ZSM-5 catalyst powder (silicon to aluminum ratio of 250), stir well, then add 1600 g of acidic silica sol, 800 g of montmorillonite, 5 g of phthalocyanine powder, 40 g of phosphoric acid.
- the aqueous slurry is prepared by thorough stirring, and the aqueous slurry is spray-dried using a centrifugal spray dryer having an inlet temperature of 300 ° C and an outlet temperature of 180 ° C.
- the aqueous slurry is The feed rate was 250 ml/min, and the obtained catalyst muffle furnace was fired in an air atmosphere at a temperature of 600 ° C for 4 hours. Catalyst 6# was obtained.
- the above Example 1 was prepared without a phosphorus-doped catalyst for comparative experiments, and Examples 2-6 were the catalysts of the present invention. The catalytic performance of these catalysts was characterized in Example
- the catalyst of the present invention has a significant improvement in the selectivity of both propylene and C4 olefins as compared with the catalyst 1# which is not miscible.
- the wear index test was carried out on the 1# catalyst and 2# catalyst using a vertical wear index tester.
- the standard was ASTM-D5757-00, and the Changling FCC balance agent was used as the control sample.
- the Changling FCC balance agent wear index was 2.5%.
- the 1# catalyst wear index was 2.1%, and the 2# catalyst wear index was 1.9%. From this, it can be seen that the catalyst of the present invention can also exhibit significantly improved wear resistance by passing the phosphorus.
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Abstract
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US14/764,923 US9856183B2 (en) | 2013-01-31 | 2014-01-29 | Catalyst with high C4 olefin selectivity for preparing olefin from methanol and preparation method thereof |
CA2899759A CA2899759A1 (en) | 2013-01-31 | 2014-01-29 | Catalyst with high c4 olefin selectivity for preparing olefin from methanol and preparation method thereof |
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WO2002032836A1 (en) * | 2000-10-13 | 2002-04-25 | Exxonmobil Chemical Patents, Inc. | Process for producing light olefins |
CN101318143A (zh) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | 制备分子筛流化床催化剂的方法 |
CN102372534A (zh) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | 含氧化合物转化制低碳烯烃的方法 |
CN103623859A (zh) * | 2013-12-06 | 2014-03-12 | 陕西煤化工技术工程中心有限公司 | 高空速下获得高丙乙比的甲醇制丙烯催化剂及其制备方法 |
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NZ191302A (en) * | 1978-09-05 | 1981-10-19 | Mobil Oil Corp | Producing hydrocarbon mixture from alcohol feed using crystalline aluminosilicate zeolite catalyst |
DE10233975A1 (de) | 2002-07-25 | 2004-02-12 | Lurgi Ag | Vorrichtung zur Herstellung von Propylen aus Methanol |
CN101172918B (zh) | 2006-11-02 | 2010-09-01 | 中国石油化工股份有限公司 | 由甲醇转化制丙烯的方法 |
CN101279280B (zh) | 2007-04-04 | 2010-07-28 | 中国石油化工股份有限公司 | 由甲醇转化制丙烯的催化剂 |
CN101274283B (zh) * | 2008-04-11 | 2011-05-18 | 中国石油化工股份有限公司 | 含氧化合物制烯烃催化剂的制备方法 |
CN101402049A (zh) | 2008-11-11 | 2009-04-08 | 上海福瑞得化工科技有限公司 | 一种甲醇制丙烯催化剂的制备方法 |
CN102211971B (zh) | 2010-04-09 | 2015-08-05 | 上海华谊(集团)公司 | 甲醇制丙烯工艺 |
CN102371168B (zh) * | 2010-08-23 | 2013-12-04 | 中国石油化工股份有限公司 | 流化床催化剂的制备方法 |
CN102531823B (zh) | 2010-12-23 | 2014-10-22 | 中国科学院金属研究所 | 一种高丙烯产率甲醇制丙烯的方法 |
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WO2002032836A1 (en) * | 2000-10-13 | 2002-04-25 | Exxonmobil Chemical Patents, Inc. | Process for producing light olefins |
CN101318143A (zh) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | 制备分子筛流化床催化剂的方法 |
CN102372534A (zh) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | 含氧化合物转化制低碳烯烃的方法 |
CN103623859A (zh) * | 2013-12-06 | 2014-03-12 | 陕西煤化工技术工程中心有限公司 | 高空速下获得高丙乙比的甲醇制丙烯催化剂及其制备方法 |
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CA2899759A1 (en) | 2014-08-07 |
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