CN112387267A - Preparation method and application of methanol conversion catalyst with magnesium aluminate spinel as carrier - Google Patents
Preparation method and application of methanol conversion catalyst with magnesium aluminate spinel as carrier Download PDFInfo
- Publication number
- CN112387267A CN112387267A CN201910743136.4A CN201910743136A CN112387267A CN 112387267 A CN112387267 A CN 112387267A CN 201910743136 A CN201910743136 A CN 201910743136A CN 112387267 A CN112387267 A CN 112387267A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- methanol conversion
- carrier
- aluminate spinel
- magnesium aluminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 444
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 143
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 239000011777 magnesium Substances 0.000 title claims abstract description 79
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 78
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 72
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 70
- 239000011029 spinel Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- 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 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 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 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 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 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- YXIXIZVWHXLIMS-UHFFFAOYSA-N cyclohexanone;cyclohexene Chemical compound C1CCC=CC1.O=C1CCCCC1 YXIXIZVWHXLIMS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- 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
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a methanol conversion catalyst taking magnesium aluminate spinel as a carrier. The preparation method of the methanol conversion catalyst with the magnesium aluminate spinel as the carrier comprises the following steps: mixing and pulping a magnesium source, an aluminum source, a binder, a molecular sieve and water to obtain an intermediate carrier containing magnesium aluminate spinel, wherein the mass ratio of the magnesium aluminate spinel to the binder to the molecular sieve is 1-80: 5-40: 30-85 parts; mixing the intermediate carrier with sulfuric acid, a silicon source, seed crystals, a template agent and water, then aging and crystallizing, and then carrying out solid-liquid separation, washing and roasting on the obtained crystallized product to obtain the methanol conversion catalyst. The methanol conversion catalyst with the magnesia-alumina spinel as the carrier provided by the invention takes the modified magnesia-alumina spinel as the carrier, can improve the methanol conversion reaction efficiency and the low-carbon olefin yield, and also widens the selection space of the methanol conversion catalyst carrier.
Description
Technical Field
The invention relates to a catalyst processing technology, in particular to a methanol conversion catalyst and a preparation method and application thereof, and especially relates to a preparation method and application of a methanol conversion catalyst taking magnesium aluminate spinel as a carrier.
Background
Ethylene and propylene are the basic organic chemicals in great demand in the petrochemical industry. Due to the gradual shortage of petroleum resources, many industrially developed countries have been intensively developing new technical routes for preparing light olefins from non-petroleum raw materials. For countries with relatively short petroleum resources and rich coal resources, the method for developing the technology of preparing low-carbon olefin from coal or natural gas through Methanol To Olefins (MTO) is of great significance, wherein the performance of the catalyst for preparing low-carbon olefin from Methanol is of great importance.
The catalyst support is an important component of the catalyst. The proper carrier can ensure that the active component is uniformly dispersed on the surface of the carrier, increase the specific surface area of the catalyst, improve the catalytic efficiency of the active component per unit mass, reduce the sintering degree of the active component in the using process and improve the thermal stability of the catalyst, so the selection of the catalyst carrier is very important.
At present, carriers of catalysts for preparing low-carbon olefins by methanol conversion are generally pseudo-boehmite and kaolin, the types of the carriers are few, and the industrial production and the popularization and the application of some catalysts are limited according to different requirements of different processes on performance indexes of the catalysts. For example: fluidized bed processes have higher requirements on the attrition index of the catalyst, while fixed beds require catalysts with sufficient stability and long life, thereby reducing the number of regenerations and extending the regeneration period. The pseudo-boehmite is widely applied in the fields of chemical industry and environmental protection due to the special structure and performance, has better thermal stability and low cost, but can be mutually converted under certain conditions because of nine forms of alumina, is a product with highest activity in hydrated alumina and most difficult to control in the production process, and is very easy to generate impurity phases in the production process to influence the repeatability of catalyst preparation. Meanwhile, strong interaction between a strong acid site on the surface of the alumina and active components often causes the active components such as nickel, cobalt and the like to generate nickel (cobalt) spinel, and the latter is difficult to sulfide to generate a sulfide-state active phase, so that the catalytic activity is reduced.
The main chemical component of kaolin is SiO2、Al2O3And other metal oxides, have good insulation properties and chemical stability, but when used as a catalyst support, in order to increase the specific surface area of kaolin, acidification treatment is generally used, but this tends to cause environmental pollution and the like. Therefore, in order to expand the selectivity of the carrier for preparing low-carbon olefin from methanol, a new material or a treatment method for preparing low-carbon olefin by methanol conversion needs to be researched, and the current situation that the carrier of the existing methanol conversion catalyst is singly selected is improved.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a methanol conversion catalyst with magnesium aluminate spinel as a carrier, which adopts modified magnesium aluminate spinel as the carrier, can widen the selection space of the carrier in the methanol conversion catalyst and improve the methanol conversion reaction efficiency.
The invention also provides a methanol conversion catalyst taking magnesium aluminate spinel as a carrier, which is prepared by adopting the preparation method. The methanol conversion catalyst can improve the methanol conversion reaction efficiency and obtain a large amount of low-carbon olefins.
The invention also provides an application of the methanol conversion catalyst taking magnesium aluminate spinel as a carrier in the preparation of low-carbon olefin through methanol conversion.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a methanol conversion catalyst using magnesium aluminate spinel as a carrier, comprising the steps of:
mixing and pulping a magnesium source, an aluminum source, a binder, a molecular sieve and water to obtain an intermediate carrier containing magnesium aluminate spinel, wherein the mass ratio of the magnesium aluminate spinel to the binder to the molecular sieve is (1-80): (5-40): (30-85);
mixing the intermediate carrier obtained in the step with sulfuric acid, a silicon source, a seed crystal, a template agent and water, then aging and crystallizing, and then carrying out solid-liquid separation, washing, drying and roasting on the obtained crystallized product to obtain a methanol conversion catalyst;
wherein the molar ratio of the sulfuric acid to the magnesium aluminate spinel is (0.01-5): 1; the molar ratio of the silicon source to the magnesium aluminate spinel calculated by silicon dioxide is (1-50): 1; the molar ratio of the silicon source to the template, water and seed crystal, calculated as silica, is 1: (0.01-20): (10-500): (0.01-50).
The magnesium aluminate spinel has two active centers of acidity and alkalinity, stable property, high thermal stability, difficult sintering and wide application in catalytic reaction, and can be used as a catalyst for certain reactions and a catalyst carrier for certain reactions. For example, magnesia-alumina spinel is used as a desulfurization catalyst and applied to a fluid catalytic cracking device to effectively remove sulfur in regenerated flue gas and sulfur in automobile exhaust; or as a cyclohexanone double polymerization catalyst, the cyclohexanone is subjected to aldol condensation and dehydration under the catalytic action of magnesium aluminate spinel to generate cyclohexene cyclohexanone; for example, magnesia alumina spinel can also be used as a good carrier of nickel-based catalysts for partial oxidation of methane.
However, there is no report on how to use magnesia-alumina spinel as a carrier for preparing a low-carbon olefin catalyst by a methanol conversion reaction to widen the selection space of the carrier in the methanol conversion catalyst and improve the methanol conversion reaction efficiency.
According to the preparation method provided by the invention, firstly, an aluminum source, a magnesium source, a molecular sieve and a binder are used as raw materials to prepare an intermediate carrier (or called as a catalyst intermediate product) containing magnesium aluminate spinel and the molecular sieve, wherein the magnesium aluminate spinel is used as a carrier, and the molecular sieve is used as an active component; and then modifying the intermediate carrier to obtain the catalyst for preparing the low-carbon olefin catalyst by methanol conversion with the modified magnesia-alumina spinel as the carrier, namely the methanol conversion catalyst with the magnesia-alumina spinel as the carrier. When the methanol conversion catalyst taking magnesium aluminate spinel as a carrier is used for preparing low-carbon olefins (particularly ethylene and propylene) by methanol conversion, the conversion rate of methanol reaches 100%, the sum of the yields of ethylene and propylene can reach more than 70%, and the sum of the yields of ethylene, propylene and butylene can reach more than 78%.
Based on the above phenomena, the inventor analyzes that, in the preparation process of the above methanol conversion catalyst, firstly, spinel is used as a carrier, an intermediate carrier (or called as a catalyst intermediate product) is obtained by bonding with a binder, and then the intermediate carrier (or called as a catalyst intermediate product) is modified, in the process of modifying the catalyst intermediate product, part of aluminum in magnesium aluminate spinel is converted into a primary structural unit of a molecular sieve, so that the carrier modification is realized, and the catalyst suitable for preparing low-carbon olefin from methanol is prepared, therefore, when the methanol conversion catalyst is used in the reaction of preparing low carbon from methanol, the yields of ethylene, propylene and butylene are high when the methanol conversion rate is 100%.
Specifically, the magnesium source may be a magnesium source commonly used in the synthesis of magnesium aluminate spinel, including but not limited to at least one of the following magnesium salts: magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium oxide.
Specifically, the aluminum source may also be a magnesium source commonly used in the synthesis of magnesium aluminate spinel, including but not limited to at least one of the following aluminum salts: sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, and pseudoboehmite.
In the invention, for convenience of expression and calculation, in the process of mixing and pulping the magnesium source, the aluminum source, the binder, the molecular sieve and water, the magnesium source and the aluminum source are considered to be completely reacted and participate in the reaction to generate the magnesium aluminate spinel, wherein the molar ratio between the magnesium element in the magnesium source and the aluminum element in the aluminum source is the molar ratio of magnesium to aluminum in the magnesium aluminate spinel.
For example, when the amount of the magnesium element in the magnesium source is x mol and the amount of the aluminum element in the aluminum source is y mol, the chemical formula of the magnesium aluminate spinel formed by the reaction of the magnesium source and the aluminum source can be expressed as MgxAlyOx+1.5y. Therefore, in the specific implementation process, the amount of the magnesium aluminate spinel in the intermediate carrier can be determined according to the adding amount of the magnesium source and the adding amount of the aluminum source.
Specifically, the molar ratio between the magnesium element in the magnesium source and the aluminum element in the aluminum source can be controlled to be generally 1: (2-100). In a preferred embodiment of the present invention, the molar ratio between the magnesium element in the magnesium source and the aluminum element in the aluminum source is generally controlled to be 1: (2-20) and further 1: (2-8), namely the molar ratio of magnesium to aluminum in the magnesium aluminate spinel is 1: (2-20) and further 1: (2-8).
In the present invention, the binder used for synthesizing the intermediate carrier may be at least one of the binders commonly used in the catalyst processing and synthesizing process, such as silica sol, alumina sol, silica alumina gel, phosphor alumina gel, etc. In the practice of the present invention, silica sol or alumina sol is generally used as the binder.
In the invention, the molecular sieve used for synthesizing the intermediate carrier can be a silicon-aluminum molecular sieve, specifically can be a certain silicon-aluminum molecular sieve, and can also be a mixture of a plurality of silicon-aluminum molecular sieves. Specifically, the molecular sieve used for synthesizing the intermediate support can be at least one selected from ZSM-5, ZSM-34, ZSM-11, SAPO-34, Y-type molecular sieve, beta molecular sieve and the like.
In a preferred embodiment of the invention, the mass ratio of the magnesium aluminate spinel to the binder to the molecular sieve is generally controlled to be (20-40): (15-27): (30-40).
In the process of modifying the intermediate carrier, the silicon source used may be specifically selected from one or more of silica sol, ethyl orthosilicate, water glass and the like.
In the present invention, the amount of the silicon source is generally determined by the amount of silicon dioxide contained in the silicon source unless otherwise specified.
In the present invention, the template used may be one commonly used in the catalyst preparation process, such as at least one of triethylamine, n-butylamine, ethylenediamine, di-n-propylamine, diisopropylamine, 1, 6-hexamethylenediamine, tetraethylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium hydroxide, tetrapropylammonium bromide, and the like.
In the present invention, the seed crystal used may be selected from the seed crystal of the silicoaluminophosphate molecular sieve, and may be one or more of the seed crystal of the silicoaluminophosphate molecular sieve, such as ZSM-5 seed crystal, ZSM-11 seed crystal, and ZSM-5 seed crystal and ZSM-11 seed crystal.
Further, the molar ratio of silicon source to templating agent, water and seed, calculated as silica, may generally be controlled to be in the range of 1: (0.1-5): (20-40): (10-50).
Reasonably controlling the modification condition of the intermediate carrier is beneficial to further improving the performance of the methanol conversion catalyst, improving the conversion rate of methanol and obtaining higher yield of low-carbon olefins such as ethylene, propylene and the like. In a preferred embodiment of the invention, the intermediate carrier is mixed with sulfuric acid, a silicon source, a seed crystal, a template agent and water, then the mixture is aged at 10-200 ℃ for at least 1 hour and crystallized at 110-200 ℃ for at least 10 hours, and the crystallized product is subjected to solid-liquid separation, washing and roasting at 450-550 ℃ for at least 2 hours to obtain the methanol conversion catalyst taking magnesium aluminate spinel as the carrier.
The aging and crystallization can be completed in a crystallization reactor, wherein the specific time of aging can be reasonably adjusted according to conditions such as aging temperature, and the like, and the aging is usually performed at 10-200 ℃ for 1-80 hours, for example, at 50-65 ℃ for 10-25 hours.
The crystallization time can also be adjusted reasonably according to the conditions such as crystallization temperature, for example, the crystallization time can be at least 10-150 hours at 110-200 ℃. In the specific implementation process of the invention, the crystallization is carried out for 24-36 hours at 150-200 ℃.
In this embodiment, how to perform solid-liquid separation on the crystallized product is not particularly limited, and most of the water in the crystallized product can be removed by a solid-liquid separation method that is conventional in the art, for example, by suction filtration.
The specific washing can adopt a deionized water washing mode; the drying can be completed in an oven, and the drying temperature can be generally set to be 80-120 ℃.
The roasting time can be reasonably determined according to conditions such as roasting temperature and the like, and can be usually roasted at 450-550 ℃ for 2-10 hours, for example, at about 500 ℃ for 5-8 hours to obtain the methanol conversion catalyst.
In a second aspect of the present invention, there is provided a methanol conversion catalyst using magnesium aluminate spinel as a carrier, which is prepared by the preparation method of the first aspect.
The inventor researches and discovers that when the methanol conversion catalyst taking magnesium aluminate spinel as a carrier is used in the reaction of converting methanol into low-carbon olefin (particularly ethylene, propylene and butylene), the conversion rate of methanol reaches 100%, the sum of the yields of ethylene and propylene can reach more than 70%, and the sum of the yields of ethylene, propylene and butylene can reach more than 78%. Therefore, the methanol conversion catalyst taking the magnesium aluminate spinel as the carrier can be beneficial to obtaining a large amount of low-carbon olefins. In addition, because the modified magnesium aluminate spinel is adopted as the carrier of the catalyst, the selection space of the carrier in the methanol conversion catalyst is widened.
The third aspect of the present invention provides an application of the methanol conversion catalyst using magnesium aluminate spinel as a carrier in the second aspect in the preparation of low carbon olefins by methanol conversion.
As mentioned above, the methanol conversion catalyst using magnesium aluminate spinel as a carrier can improve the methanol conversion rate, and the yield of low-carbon olefins (ethylene, propylene and butylene) is high, so that the catalyst can be well used in the reaction of preparing low-carbon olefins by methanol conversion to obtain a large amount of low-carbon olefins.
In the specific implementation process of the invention, the methanol conversion catalyst with magnesium aluminate spinel as a carrier can be aged firstly, then the catalyst is filled into a reactor, methanol-containing gas or pure methanol gas is introduced, the reaction pressure can be controlled at normal pressure, and the reaction temperature can be controlled at about 450 ℃, so that the full conversion of methanol is realized, a large amount of low-carbon olefins such as ethylene, propylene, butylene and the like are obtained, and particularly a large amount of ethylene and propylene can be obtained.
The preparation method of the methanol conversion catalyst with the magnesium aluminate spinel as the carrier provided by the invention has the advantages that the modified magnesium aluminate spinel is used as the carrier of the methanol conversion catalyst, and when the modified magnesium aluminate spinel is used for converting low-carbon olefin into methanol, the conversion rate of the methanol can reach 100%; the sum of the yields of ethylene and propylene can reach more than 70 percent, and is usually 70 to 80 percent; the sum of the yields of ethylene, propylene and butylene can reach more than 78 percent, and generally can reach 78 to 86 percent.
In addition, because the modified magnesia-alumina spinel is used as a carrier, the limitation that the traditional methanol conversion catalyst can only adopt pseudoboehmite and kaolin is broken through.
In addition, the preparation method has simple and environment-friendly process conditions and simple steps, and the raw materials are all cheap materials, so the production and processing cost of the methanol conversion catalyst can be effectively reduced.
The methanol conversion catalyst with the magnesia-alumina spinel as the carrier provided by the invention takes the modified magnesia-alumina spinel as the carrier, thereby not only widening the selection space of the carrier in the methanol conversion catalyst, but also ensuring that the methanol conversion rate reaches 100%, the sum of the yields of ethylene and propylene can reach 70-80%, and the sum of the yields of ethylene, propylene and butylene can reach 78-86%. Therefore, the method can be well applied to the preparation of the low-carbon olefin by the conversion of the methanol, realize the full conversion of the methanol and obtain a large amount of the low-carbon olefin.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Example 1
The embodiment provides a methanol conversion catalyst using magnesium aluminate spinel as a carrier, and the preparation method comprises the following steps:
2g of magnesium nitrate and 30.2g of aluminum nitrate are dissolved in 20g of water, 5g of ZSM-5 molecular sieve and 3g of silica sol binder are added, and the mixture is mixed and stirred at a temperature of about 10 ℃ for about 4 hours to prepare the intermediate carrier.
Mixing the prepared intermediate carrier with 28mL of sulfuric acid solution with the concentration of 0.5mol/L, 25g of silica sol, 20g of n-butylamine, 2g of ZSM-5 seed crystal and 30g of water, then aging at 50 ℃ for about 10h, crystallizing at 200 ℃ for about 24h, and finally filtering, washing and roasting at 500 ℃ for about 8h to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesium aluminate spinel as carrier prepared in this example was evaluated according to the following procedures:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: methanol conversion 100%, ethylene (C)2 ＝) Yield 32% of propylene (C)3 ＝) Yield 42% of butene (C)4 ＝) The yield was 7.5%, the sum of the yields of ethylene and propylene (i.e.C)2-3 ＝Yield) was 74%, the sum of the yields of ethylene, propylene and butene (i.e. C)2-4 ＝Yield) was 82%.
Specific methanol conversions, as well as ethylene, propylene and butene conversions are shown in table 1.
Example 2
The embodiment provides a methanol conversion catalyst using magnesium aluminate spinel as a carrier, and the preparation method comprises the following steps:
5g of magnesium chloride and 23g of aluminum chloride are dissolved in 40g of water, 11g of SAPO-34 molecular sieve and 7g of alumina sol binder are added, and the mixture is stirred at the temperature of about 15 ℃ for about 4 hours to prepare the intermediate carrier.
Mixing the prepared intermediate carrier with 10mL of sulfuric acid solution with the concentration of 0.3mol/L, 60g of ethyl orthosilicate, 50g of ethylenediamine, 2g of ZSM-5 seed crystal, 2g of ZSM-11 seed crystal and 50g of water, then aging at 50 ℃ for about 20 hours, crystallizing at 190 ℃ for about 24 hours, and finally filtering, washing and roasting at 500 ℃ for about 5 hours to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesium aluminate spinel as carrier prepared in this example was evaluated according to the following procedures:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: conversion of methanol is 100%, C2 ＝Yield 36%, C3 ＝Yield 43%, C4 ＝Yield 6%, C2-3 ＝Yield 79%, C2-4 ＝The yield thereof was found to be 85%.
Specific methanol conversion, and ethylene (C)2 ＝) Propylene (C)3 ＝) And butene (C)4 ＝) The conversion of (b) is shown in table 1.
Example 3
The embodiment provides a methanol conversion catalyst using magnesium aluminate spinel as a carrier, and the preparation method comprises the following steps:
dissolving 3g of magnesium nitrate and 18g of aluminum nitrate in 40g of water, adding 11g of ZSM-5 molecular sieve and 7g of aluminum sol binder, and mixing at the temperature of about 20 ℃ for 4 hours to prepare the intermediate carrier.
Mixing the intermediate carrier with 5mL of 0.3mol/L sulfuric acid solution, 60g of ethyl orthosilicate, 50g of ethylenediamine, 2g of ZSM-5 seed crystal, 2g of ZSM-11 seed crystal and 50g of water, then aging at 50 ℃ for about 20 hours, crystallizing at 190 ℃ for about 24 hours, and finally filtering, washing and roasting at 500 ℃ for 5 hours to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesium aluminate spinel as carrier prepared in this example was evaluated according to the following procedures:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: conversion of methanol is 100%, C2 ＝Yield 32%, C3 ＝Yield 40%, C4 ＝Yield 7%, C2-3 ＝Yield 72%, C2-4 ＝The yield thereof was found to be 79%.
Specific methanol conversion, and ethylene (C)2 ＝) Propylene (C)3 ＝) And butene (C)4 ＝) The conversion of (b) is shown in table 1.
Example 4
The embodiment provides a methanol conversion catalyst using magnesium aluminate spinel as a carrier, and the preparation method comprises the following steps:
1.5g of magnesium carbonate and 27g of aluminum acetate are dissolved in 27g of water, 4g of ZSM-11 molecular sieve, 4g of SAPO-34 molecular sieve and 5g of silica sol binder are added, and the mixture is stirred for 3 hours at 20 ℃ to prepare the intermediate carrier.
The prepared intermediate carrier is mixed with 40mL of sulfuric acid solution with the concentration of 0.1mol/L, 50g of water glass (the content of silicon dioxide is 27 percent), 30g of 1,6 hexamethylene diamine, 2g of ZSM-5 seed crystal, 1g of ZSM-11 seed crystal and 40g of water, then the mixture is aged at 65 ℃ for about 12 hours, crystallized at 170 ℃ for about 36 hours, and finally filtered, washed and roasted at 500 ℃ for 5 hours to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesium aluminate spinel as carrier prepared in this example was evaluated according to the following procedures:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: conversion of methanol is 100%, C2 ＝Yield 35%, C3 ＝Yield 43%, C4 ＝Yield 8%, C2-3 ＝Yield 78%, C2-4 ＝The yield thereof was found to be 86%.
Specific methanol conversion, and ethylene (C)2 ＝) Propylene (C)3 ＝) And butene (C)4 ＝) The conversion of (b) is shown in table 1.
Comparative example 1
This comparative example provides a methanol conversion catalyst, which was prepared as follows:
4g of magnesium nitrate and 20.2g of aluminum nitrate were dissolved in 20g of water, 5g of ZSM-5 molecular sieve and 3g of silica sol were added, and the mixture was stirred at 10 ℃ for 4 hours to prepare a methanol conversion catalyst.
The methanol conversion catalyst prepared in the comparative example was evaluated in the following procedure:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: conversion of methanol 98%, C2 ＝Yield 30%, C3 ＝Yield of37% of C4 ＝Yield 7%, C2-3 ＝Yield 67%, C2-4 ＝The yield thereof was found to be 74%.
Specific methanol conversion, and ethylene (C)2 ＝) Propylene (C)3 ＝) And butene (C)4 ＝) The conversion of (b) is shown in table 1.
Comparative example 2
The comparative example provides a method for preparing a methanol conversion catalyst using kaolin as a carrier, comprising:
9.5g of kaolin and 3.5g of ZSM-5 molecular sieve are dispersed in 20g of water, 3g of silica sol is added, and the mixture is stirred at 10 ℃ for 4 hours to prepare the methanol conversion catalyst.
The methanol conversion catalyst prepared in the comparative example was evaluated in the following procedure:
firstly, aging a methanol conversion catalyst in 100 percent steam at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to carry out a methanol conversion experiment. Wherein, the loading amount of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, pure methanol is fed, and the feeding amount is 0.16 g/min. The product yield is based on the amount of hydrocarbon after dehydration of methanol.
Catalyst evaluation showed that: conversion of methanol 99%, C2 ＝Yield 27%, C3 ＝Yield 38%, C4 ＝Yield 8%, C2-3 ＝Yield 65%, C2-4 ＝The yield thereof was found to be 73%.
Specific methanol conversion, and ethylene (C)2 ＝) Propylene (C)3 ＝) And butene (C)4 ＝) The conversion of (b) is shown in table 1.
TABLE 1
As can be seen from Table 1, the methanol conversion of examples 1-4 reached 100%, which is higher than 98% for comparative example 1 and 99% for comparative example 2.
Also, the ethylene yield and the propylene yield of examples 1 to 4 are very significantly advantageous compared to comparative example 1 and comparative example 2, and thus the sum of the ethylene and propylene yields (C)2-3 ＝) Obviously outstanding, reaching 70 percent to 80 percent, compared with C of comparative example 1 and comparative example 22-3 ＝The yield is not up to 70%; in addition, compared with comparative example 1 and comparative example 2, the sum of the ethylene yield, the propylene yield and the butene yield of examples 1-4 is also higher, reaching 78-86%, which is obviously higher than 74% of comparative example 1 and 73% of comparative example 2.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a methanol conversion catalyst taking magnesium aluminate spinel as a carrier is characterized by comprising the following steps:
mixing and pulping a magnesium source, an aluminum source, a binder, a molecular sieve and water to obtain an intermediate carrier containing magnesium aluminate spinel, wherein the mass ratio of the magnesium aluminate spinel to the binder to the molecular sieve is 1-80: 5-40: 30-85 parts;
mixing the intermediate carrier with sulfuric acid, a silicon source, a seed crystal, a template agent and water, then aging and crystallizing, and then carrying out solid-liquid separation, washing, drying and roasting on the obtained crystallized product to obtain a methanol conversion catalyst taking magnesium aluminate spinel as a carrier;
wherein the molar ratio of the sulfuric acid to the magnesium aluminate spinel is 0.01-5: 1; calculated by silicon dioxide, the molar ratio of the silicon source to the magnesium aluminate spinel is 1-50: 1; the molar ratio of the silicon source to the template, water and seed crystal, calculated as silica, is 1: 0.01-20: 10-500: 0.01 to 50.
2. The production method according to claim 1, wherein the magnesium source is selected from at least one of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium carbonate, and magnesium oxide;
the aluminum source is selected from at least one of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate and pseudo-boehmite;
the binder is selected from at least one of silica sol, alumina sol, silica-alumina gel and phosphor-alumina gel;
the molecular sieve is selected from at least one of the silico-aluminum molecular sieves.
3. The production method according to claim 1, wherein the molar ratio between the magnesium element in the magnesium source and the aluminum element in the aluminum source is 1: 2 to 8.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the magnesium aluminate spinel to the binder to the molecular sieve is 20-40: 15-27: 30-40.
5. The preparation method according to claim 1, wherein the silicon source is selected from one or more of silica sol, tetraethoxysilane and water glass;
the template agent is at least one selected from triethylamine, n-butylamine, ethylenediamine, di-n-propylamine, diisopropylamine, 1, 6-hexamethylenediamine, tetraethylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium hydroxide and tetrapropylammonium bromide.
6. The method of claim 1 or 5, wherein the seed crystal is selected from a seed crystal of a silicoaluminophosphate molecular sieve.
7. Preparation method according to claim 1 or 5, characterized in that the molar ratio between the silicon source and the templating agent, water and seeds, expressed as silica, is 1: 0.1-5: 20-40: 10 to 50.
8. The method according to any one of claims 1 to 7, wherein the intermediate carrier is mixed with sulfuric acid, a silicon source, a seed crystal, a template agent and water, then aged at 10 to 200 ℃ for at least 1 hour, crystallized at 110 to 200 ℃ for at least 10 hours, and the obtained crystallized product is subjected to solid-liquid separation, washing and calcination at 450 to 550 ℃ for at least 2 hours to obtain the methanol conversion catalyst.
9. A methanol conversion catalyst using magnesium aluminate spinel as a carrier, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The use of the magnesium aluminate spinel supported methanol conversion catalyst of claim 9 in the conversion of methanol to lower olefins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910743136.4A CN112387267B (en) | 2019-08-13 | 2019-08-13 | Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910743136.4A CN112387267B (en) | 2019-08-13 | 2019-08-13 | Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112387267A true CN112387267A (en) | 2021-02-23 |
| CN112387267B CN112387267B (en) | 2023-06-30 |
Family
ID=74602448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910743136.4A Active CN112387267B (en) | 2019-08-13 | 2019-08-13 | Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112387267B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020098141A1 (en) * | 2000-11-22 | 2002-07-25 | Haldor Topsoe A/S | Process for the catalytic oxidation of carbonaceous compounds |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105195169A (en) * | 2015-10-13 | 2015-12-30 | 上海交通大学 | Catalyst for preparing light olefins through Fischer-Tropsch synthesis as well as preparation method and application of catalyst |
| CN105664903A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method of low-carbon alkane dehydrogenation catalyst carrier |
| WO2017197548A1 (en) * | 2016-05-16 | 2017-11-23 | 华电煤业集团有限公司 | Catalyst of methanol or dimethyl ether conversion to prepare aromatic hydrocarbon in situ synthesis method and application |
| CN109513457A (en) * | 2018-11-22 | 2019-03-26 | 中国石油大学(华东) | To be modified magnesium aluminate spinel as molecular sieve catalyst of carrier and preparation method thereof |
-
2019
- 2019-08-13 CN CN201910743136.4A patent/CN112387267B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020098141A1 (en) * | 2000-11-22 | 2002-07-25 | Haldor Topsoe A/S | Process for the catalytic oxidation of carbonaceous compounds |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105664903A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method of low-carbon alkane dehydrogenation catalyst carrier |
| CN105195169A (en) * | 2015-10-13 | 2015-12-30 | 上海交通大学 | Catalyst for preparing light olefins through Fischer-Tropsch synthesis as well as preparation method and application of catalyst |
| WO2017197548A1 (en) * | 2016-05-16 | 2017-11-23 | 华电煤业集团有限公司 | Catalyst of methanol or dimethyl ether conversion to prepare aromatic hydrocarbon in situ synthesis method and application |
| CN109513457A (en) * | 2018-11-22 | 2019-03-26 | 中国石油大学(华东) | To be modified magnesium aluminate spinel as molecular sieve catalyst of carrier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张超武等: "镁铝尖晶石催化剂载体的制备及表征", 《陕西科技大学学报(自然科学版)》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112387267B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927213A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN109331865B (en) | Preparation method and application of catalyst for preparing ethanol and co-producing methanol by synthesis gas one-step method | |
| TW200304427A (en) | High silica chabazite, its synthesis and its use in the conversion of oxygenates to olefins | |
| CN108160101B (en) | A kind of methanol-to-olefin catalyst and its preparation method and application | |
| CN109513457B (en) | Molecular sieve catalyst with modified magnesium aluminate spinel as carrier and preparation method thereof | |
| US20070032379A1 (en) | Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst | |
| CN103878015B (en) | For the molecular sieve catalyst and preparation method thereof of preparing propylene from methanol | |
| JP4823655B2 (en) | Method for producing xylenes | |
| CN101554592A (en) | Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst | |
| US3523092A (en) | Method of preparing supported crystalline alumino-silicate zeolites | |
| CN101684059A (en) | Method for producing propylene and ethylene through catalytic cracking of olefins | |
| KR100996976B1 (en) | Long-time catalyst for ??? reaction and Preparing method thereof | |
| CN108569707B (en) | Multi-stage pore SAPO-34 molecular sieve and application thereof in methanol-to-olefin reaction | |
| US8907151B2 (en) | Conversion of methane to aromatic compounds using UZM-39 aluminosilicate zeolite | |
| KR100891001B1 (en) | Preparation method of zsm-5/sapo-34 composite catalyst and the use thereof for the conversion of oxygenates to light olefins | |
| CN112387267B (en) | Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier | |
| CN112206811B (en) | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof | |
| RU2004120548A (en) | HYDROCARBON STEAM CRACKING CATALYST FOR PRODUCING OLEFINS, METHOD FOR ITS PREPARATION AND METHOD FOR PRODUCING OLEFINS USING THIS CATALYST | |
| KR20190056446A (en) | Molecular sieves SSZ-107, its synthesis and use | |
| CN113751057A (en) | Preparation and application of Silicalite-1 and silica-coated ZSM-5 catalyst | |
| KR102023246B1 (en) | Method for selectively enhancing yield of C4-C6 olefin and paraffin in MTO reaction using FER zeolite catalyst with cerium oxide | |
| CN108970636B (en) | Preparation method of benzene alkylation catalyst | |
| EP0036683B1 (en) | Process for the preparation of crystalline aluminium silicates, crystalline aluminium silicates so prepared and process for the production of an aromatic hydrocarbon mixture | |
| KR100888467B1 (en) | Preparation method of composite catalyst and the use thereof for the conversion of oxygenates to light olefins | |
| JP2005104912A (en) | Method for manufacturing lower olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |