CN112387267B - Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier - Google Patents
Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier Download PDFInfo
- Publication number
- CN112387267B CN112387267B CN201910743136.4A CN201910743136A CN112387267B CN 112387267 B CN112387267 B CN 112387267B CN 201910743136 A CN201910743136 A CN 201910743136A CN 112387267 B CN112387267 B CN 112387267B
- Authority
- CN
- China
- Prior art keywords
- magnesia
- methanol conversion
- carrier
- alumina spinel
- conversion catalyst
- 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.)
- Active
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 447
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 140
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011029 spinel Substances 0.000 title claims abstract description 69
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- 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 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000032683 aging Effects 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 magnesium aluminate Chemical class 0.000 claims description 17
- 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 9
- 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-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
- 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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 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
- 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
- 238000001354 calcination Methods 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
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 235000012239 silicon dioxide 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
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 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
- 238000011068 loading method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 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 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 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
- 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas 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
- 239000013067 intermediate product Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 magnesia-alumina spinel as a carrier. The preparation method of the methanol conversion catalyst taking magnesia-alumina spinel as a 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 magnesia-alumina spinel, wherein the mass ratio of the magnesia-alumina spinel to the binder to the molecular sieve is (1-80): 5-40: 30-85; mixing the intermediate carrier with sulfuric acid, a silicon source, a seed crystal, a template agent and water, aging and crystallizing, and performing solid-liquid separation, washing and roasting on the obtained crystallized product to obtain the methanol conversion catalyst. The methanol conversion catalyst taking 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 magnesia-alumina spinel as a carrier.
Background
Ethylene and propylene are basic organic chemical raw materials with high demand in petrochemical industry. Because of the growing shortage of petroleum resources, many industrially developed countries have concentrated efforts to develop new technological routes for the production of light olefins from non-petroleum feedstocks. The method has important significance for developing the technology of preparing the low-carbon olefin from the coal or the natural gas through the methanol (Methanol to Olefins, MTO) in the countries with relatively shortage of petroleum resources and relatively abundant coal resources in China, wherein the performance of the catalyst for preparing the low-carbon olefin from the methanol is important.
The catalyst support is an important component of the catalyst. The proper carrier can uniformly disperse the active components on the surface of the carrier, increase the specific surface area of the catalyst, improve the catalytic efficiency of the active components in unit mass, reduce the sintering degree of the active components in the use process and improve the thermal stability of the catalyst, so the selection of the catalyst carrier is important.
At present, carriers of the catalyst for preparing the low-carbon olefin by converting methanol are generally pseudo-boehmite and kaolin, the types of the carriers are few, and meanwhile, according to different requirements of different processes on catalyst performance indexes, the industrial production and popularization and application of some catalysts are limited. For example: the fluidized bed process has higher requirements on the attrition index of the catalyst, while the fixed bed requires the stability and the service life of the catalyst to be long enough, thereby reducing the regeneration times and prolonging the regeneration period. Because of its special structure and performance, pseudo-boehmite is widely used in the fields of chemical industry and environmental protection, has better thermal stability and low cost, but because alumina has nine forms, it can be mutually converted under a certain condition, and pseudo-boehmite is a product with highest activity in hydrated alumina and most difficult to control in the production process, and is very easy to generate heterogeneous phase in the production process, so that the repeatability of catalyst preparation is affected. Meanwhile, the strong interaction between the strong acid sites on the surface of the alumina and the active components often causes the active components such as nickel, cobalt and the like to generate nickel (cobalt) spinel, and the nickel (cobalt) spinel is difficult to be vulcanized to generate a vulcanized active phase, so that the catalytic activity is reduced.
Gao LingThe main chemical component of the soil is SiO 2 、Al 2 O 3 And other metal oxides, which have good insulation and chemical stability, but when used as a catalyst support, are generally subjected to an acidification treatment in order to increase the specific surface area of kaolin, which 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, new materials or treatment methods for preparing low-carbon olefin from methanol need to be researched, and the current situation that the existing carrier for the methanol conversion catalyst is single in choice is improved.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a methanol conversion catalyst with magnesia-alumina spinel as a carrier, which adopts modified magnesia-alumina spinel as the carrier, so that the selection space of the carrier in the methanol conversion catalyst can be widened, and the methanol conversion reaction efficiency can be improved.
The invention also provides a methanol conversion catalyst taking magnesia-alumina 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 olefin.
The invention also provides application of the methanol conversion catalyst taking the magnesia-alumina spinel as a carrier in preparing 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 magnesia-alumina 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 magnesia-alumina spinel, wherein the mass ratio of the magnesia-alumina spinel to the binder to the molecular sieve is (1-80): (5-40): (30-85);
mixing the intermediate carrier obtained in the above steps with sulfuric acid, a silicon source, a seed crystal, a template agent and water, aging, crystallizing, and performing solid-liquid separation, washing, drying and roasting on the obtained crystallized product to obtain a methanol conversion catalyst;
wherein, the mol ratio of sulfuric acid to magnesia-alumina spinel is (0.01-5): 1, a step of; the mole ratio between the silicon source and the magnesia-alumina spinel calculated by the silicon dioxide is (1-50): 1, a step of; the molar ratio between the silicon source and the template, water and seed, calculated as silica, is 1: (0.01-20): (10-500): (0.01-50).
The magnesia-alumina spinel has two active centers of acidity and alkalinity, has stable property, high thermal stability and difficult sintering, has 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 flow catalytic cracking device, so that sulfur in regenerated flue gas and sulfur in automobile exhaust are effectively removed; or as cyclohexanone double polymerization catalyst, the cyclohexanone is condensed and dehydrated by aldol under the catalysis of magnesia-alumina spinel to generate cyclohexene cyclohexanone; for example, magnesia alumina spinel can be used as a good carrier of nickel-based catalysts for partial oxidation of methane.
However, how to use magnesia-alumina spinel as a carrier of a catalyst for preparing low-carbon olefin by a methanol conversion reaction so as to widen the selection space of the carrier in the methanol conversion catalyst and improve the efficiency of the methanol conversion reaction has not been reported.
According to the preparation method provided by the invention, firstly, an aluminum source, a magnesium source, a molecular sieve and a binder are adopted as raw materials to prepare an intermediate carrier (or called a catalyst intermediate product) containing magnesia-alumina spinel and the molecular sieve, wherein the magnesia-alumina spinel is used as the carrier, and the molecular sieve is used as an active component; and then modifying the intermediate carrier to obtain the catalyst of the catalyst for preparing the low-carbon olefin by converting the methanol with the modified magnesia-alumina spinel as the carrier, namely the catalyst for converting the methanol with the magnesia-alumina spinel as the carrier. When the methanol conversion catalyst taking the magnesia-alumina spinel as the carrier is used for preparing low-carbon olefin (especially ethylene and propylene) through methanol conversion, the methanol conversion rate 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%.
The inventors analyzed based on the above phenomenon that, in the preparation process of the above methanol conversion catalyst, spinel was first used as a support, an intermediate support (or referred to as a catalyst intermediate) was obtained by binding with a binder, then the intermediate support (or referred to as a catalyst intermediate) was modified, and in the modification process of the catalyst intermediate, part of aluminum in magnesia alumina spinel was converted into a primary structural unit of a molecular sieve, thereby realizing the support modification, and a catalyst suitable for methanol to light olefins was obtained, and therefore, when the methanol conversion catalyst was used in a methanol to light reaction, the yields of ethylene, propylene and butene were high when the methanol conversion was 100%.
In particular, 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, and 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 pseudo-boehmite.
In the invention, for convenience of expression and calculation, in the process of mixing and pulping a magnesium source, an aluminum source, a binder, a molecular sieve and water, the magnesium source and the aluminum source are considered to be completely reacted to participate in the reaction and generate the magnesia-alumina 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 the magnesia-alumina in the magnesia-alumina spinel.
For example, if the amount of the substance of the magnesium element in the magnesium source is x mol and the amount of the substance 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 Mg x Al y O x+1.5y . Thus, in the practice, the amount of magnesium aluminate spinel in the intermediate support may be determined based on the amount of magnesium source added and the amount of aluminum source added.
Specifically, the molar ratio between the magnesium element in the magnesium source and the aluminum element in the aluminum source can be generally controlled to be 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), further 1: (2-8), namely, the molar ratio between magnesium and aluminum in the magnesia-alumina spinel is 1: (2-20), further 1: (2-8).
In the present invention, the binder used for synthesizing the intermediate carrier may be at least one binder commonly used in the catalyst processing and synthesizing process, such as silica sol, alumina sol, silica alumina gel, and alumina phosphate gel. In the practice of the invention, silica sol or alumina sol is typically used as the binder.
In the invention, the molecular sieve used for synthesizing the intermediate carrier can be a silicon-aluminum molecular sieve, in particular can be a certain silicon-aluminum molecular sieve or can be a mixture of a plurality of silicon-aluminum molecular sieves. Specifically, the molecular sieve used for synthesizing the intermediate carrier 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 present invention, the mass ratio between the magnesia-alumina spinel, the binder and the molecular sieve is generally controlled to be (20 to 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, tetraethyl 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 at least one of templates commonly used in the catalyst preparation process, such as triethylamine, n-butylamine, ethylenediamine, di-n-propylamine, diisopropylamine, 1, 6-hexamethylenediamine, tetraethylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium hydroxide, tetrapropylammonium bromide, etc.
In the present invention, the seed crystal used may be specifically selected from the seeds of a silica-alumina molecular sieve, and may be specifically one or more of the seeds of a silica-alumina molecular sieve, such as ZSM-5 seed crystal, ZSM-11 seed crystal, and may also be ZSM-5 seed crystal and ZSM-11 seed crystal.
Further, the molar ratio between the silicon source and the templating agent, water and seed, calculated as silica, can generally be controlled at 1: (0.1-5): (20-40): (10-50).
The modification condition of the intermediate carrier is reasonably controlled, which is favorable for further improving the performance of the methanol conversion catalyst, improving the methanol conversion rate and obtaining higher yields of low-carbon olefins such as ethylene, propylene and the like. In a preferred embodiment of the present invention, the intermediate carrier is mixed with sulfuric acid, a silicon source, a seed crystal, a template agent and water, aged at 10-200 ℃ for at least 1 hour, 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 using magnesia-alumina spinel as a carrier.
Wherein, the aging and crystallization can be completed in a crystallization reaction kettle, wherein the specific time of the aging can be reasonably adjusted according to the conditions of the aging temperature and the like, and the aging is usually carried out for 1 to 80 hours at the temperature of 10 to 200 ℃, for example, the aging can be carried out for 10 to 25 hours at the temperature of 50 to 65 ℃.
The crystallization time can be reasonably adjusted 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 implementation process of the invention, the crystallization is carried out for 24 to 36 hours at the temperature of 150 to 200 ℃.
In this embodiment, the solid-liquid separation of 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 conventional in the art, for example, by suction filtration.
The specific washing can be carried out by adopting a deionized water washing mode; drying may be accomplished in an oven, and generally may be set at a drying temperature of 80-120 ℃.
The calcination time may be reasonably determined according to conditions such as the calcination temperature, and may be usually conducted at 450 to 550℃for 2 to 10 hours, for example, at about 500℃for 5 to 8 hours, to obtain the methanol conversion catalyst.
In a second aspect, the invention provides a methanol conversion catalyst using magnesia-alumina spinel as a carrier, which is prepared by the preparation method in the first aspect.
The inventor researches and discovers that the methanol conversion catalyst taking the magnesia-alumina spinel as the carrier is used in the reaction of converting the methanol into the low-carbon olefin (especially ethylene, propylene and butylene), the conversion rate of the methanol reaches 100 percent, the sum of the yields of the ethylene and the propylene can reach more than 70 percent, and the sum of the yields of the ethylene, the propylene and the butylene can reach more than 78 percent. Therefore, the methanol conversion catalyst taking the magnesia-alumina spinel as the carrier can be beneficial to obtaining a large amount of low-carbon olefins. In addition, the modified magnesia-alumina spinel is adopted as the carrier of the catalyst, so that the selection space of the carrier in the methanol conversion catalyst is widened.
In a third aspect, the invention provides the use of the magnesia-alumina spinel supported methanol conversion catalyst in the second aspect in the preparation of lower olefins by methanol conversion.
As described above, the methanol conversion catalyst using magnesium aluminate spinel as a carrier can improve the methanol conversion rate and has a higher yield of low-carbon olefins (ethylene, propylene and butene), 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 implementation process of the invention, the methanol conversion catalyst taking the magnesia-alumina spinel as the carrier can be firstly subjected to aging treatment, then filled into a reactor, and introduced with methanol-containing gas or pure methanol gas, 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.
According to the preparation method of the methanol conversion catalyst taking the magnesia-alumina spinel as the carrier, the modified magnesia-alumina spinel is taken as the carrier of the methanol conversion catalyst, and when the catalyst is used for converting the methanol into the low-carbon olefin, the methanol conversion rate can reach 100 percent; 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 can reach 78 to 86 percent generally.
In addition, because the modified magnesia-alumina spinel is used as a carrier, the limitation that the traditional methanol conversion catalyst can only adopt pseudo-boehmite and kaolin is broken through.
In addition, the preparation method has the advantages of simple and environment-friendly process conditions, simple steps and cheaper raw materials, so that the production and processing cost of the methanol conversion catalyst can be effectively reduced.
The methanol conversion catalyst taking the magnesia-alumina spinel as the carrier provided by the invention takes the modified magnesia-alumina spinel as the carrier, not only expands the selection space of the carrier in the methanol conversion catalyst, but also ensures 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 low-carbon olefin by methanol conversion, realizes the full conversion of methanol and obtains a large amount of low-carbon olefin.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
The embodiment provides a methanol conversion catalyst taking magnesia-alumina 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 for about 4 hours at the temperature of about 10 ℃ to prepare an intermediate carrier.
The prepared intermediate carrier is mixed 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 aged at 50 ℃ for about 10 hours, crystallized at 200 ℃ for about 24 hours, filtered and washed, and finally baked at 500 ℃ for about 8 hours to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesia-alumina spinel as a carrier prepared in the example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: the methanol conversion was 100%, ethylene (C 2 ＝ ) Yield 32%, propylene (C) 3 ＝ ) Yield 42%, butene (C) 4 ＝ ) Yield 7.5%, sum of ethylene and propylene yields (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%.
The specific methanol conversion and the conversion of ethylene, propylene and butene are shown in table 1.
Example 2
The embodiment provides a methanol conversion catalyst taking magnesia-alumina spinel as a carrier, and the preparation method comprises the following steps:
5g of magnesium chloride and 23g of aluminum chloride were dissolved in 40g of water, and 11g of SAPO-34 molecular sieve, 7g of aluminum sol binder were added thereto, and stirred at a temperature of about 15℃for about 4 hours to prepare an intermediate carrier.
The prepared intermediate carrier is mixed with 10mL of sulfuric acid solution with the concentration of 0.3mol/L, 60g of tetraethoxysilane, 50g of ethylenediamine, 2g of ZSM-5 seed crystal, 2g of ZSM-11 seed crystal and 50g of water, then aged for about 20 hours at 50 ℃, crystallized for about 24 hours at 190 ℃, filtered, washed and roasted for about 5 hours at 500 ℃ to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesia-alumina spinel as a carrier prepared in the example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: the conversion of methanol is 100%, C 2 ＝ Yield is 36%, C 3 ＝ Yield is 43%, C 4 ＝ Yield 6%, C 2-3 ＝ Yield is 79%, C 2-4 ＝ 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 (2) is shown in Table 1.
Example 3
The embodiment provides a methanol conversion catalyst taking magnesia-alumina spinel as a carrier, and the preparation method comprises the following steps:
3g of magnesium nitrate and 18g of aluminum nitrate are dissolved in 40g of water, 11g of ZSM-5 molecular sieve and 7g of aluminum sol binder are added, and the mixture is mixed for 4 hours at the temperature of about 20 ℃ to prepare an intermediate carrier.
The intermediate carrier is mixed with 5mL of sulfuric acid solution with the concentration of 0.3mol/L, 60g of tetraethoxysilane, 50g of ethylenediamine, 2g of ZSM-5 seed crystal, 2g of ZSM-11 seed crystal and 50g of water, then aged for about 20 hours at 50 ℃, crystallized for about 24 hours at 190 ℃, and finally filtered, washed and roasted for 5 hours at 500 ℃ to obtain the methanol conversion catalyst.
The methanol conversion catalyst using magnesia-alumina spinel as a carrier prepared in the example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: the conversion of methanol is 100%, C 2 ＝ Yield is 32%, C 3 ＝ Yield 40%, C 4 ＝ Yield 7%, C 2-3 ＝ Yield is 72%, C 2-4 ＝ 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 (2) is shown in Table 1.
Example 4
The embodiment provides a methanol conversion catalyst taking magnesia-alumina spinel as a carrier, and the preparation method comprises the following steps:
1.5g of magnesium carbonate and 27g of aluminum acetate are taken and 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 an intermediate carrier.
The prepared intermediate carrier was mixed with 40mL of sulfuric acid solution having a concentration of 0.1mol/L, 50g of water glass (silica content: 27%), 30g of 1,6 hexamethylenediamine, 2g of ZSM-5 seed crystal, 1g of ZSM-11 seed crystal and 40g of water, then aged at 65℃for about 12 hours, crystallized at 170℃for about 36 hours, and finally filtered, washed and calcined at 500℃for 5 hours to obtain a methanol conversion catalyst.
The methanol conversion catalyst using magnesia-alumina spinel as a carrier prepared in the example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: the conversion of methanol is 100%, C 2 ＝ Yield is 35%, C 3 ＝ Yield is 43%, C 4 ＝ Yield is 8%, C 2-3 ＝ Yield is 78%, C 2-4 ＝ 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 (2) is shown in Table 1.
Comparative example 1
This comparative example provides a methanol conversion catalyst, which is prepared as follows:
4g of magnesium nitrate and 20.2g of aluminum nitrate are dissolved in 20g of water, 5g of ZSM-5 molecular sieve and 3g of silica sol are added, and the mixture is stirred at 10 ℃ for 4 hours to prepare the methanol conversion catalyst.
The methanol conversion catalyst prepared in this comparative example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: the conversion rate of methanol is 98%, C 2 ＝ Yield is 30%, C 3 ＝ Yield is 37%, C 4 ＝ Yield 7%, C 2-3 ＝ Yield 67%, C 2-4 ＝ 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 (2) is shown in Table 1.
Comparative example 2
The comparative example provides a method for preparing a methanol conversion catalyst with kaolin as a carrier, which comprises the following steps:
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 for 4 hours at 10 ℃ to prepare the methanol conversion catalyst.
The methanol conversion catalyst prepared in this comparative example was evaluated as follows:
firstly, aging a methanol conversion catalyst in 100% water vapor at 700 ℃ for 4 hours, then filling the methanol conversion catalyst in a small fixed fluidized bed reactor, and introducing methanol to perform a methanol conversion experiment. Wherein, the loading of the methanol conversion catalyst is 3g, the reaction pressure is normal pressure, the reaction temperature is 450 ℃, and the feeding amount of pure methanol is 0.16g/min. The yield of the product is based on the hydrocarbon content after dehydration of the methanol.
The catalyst evaluation shows that: methanol conversion of 99%, C 2 ＝ Yield 27%, C 3 ＝ Yield 38%, C 4 ＝ Yield is 8%, C 2-3 ＝ The yield is 65%, C 2-4 ＝ 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 (2) 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 yields and the propylene yields of examples 1 to 4 have very significant advantages compared with comparative examples 1 and 2, so that the sum of the ethylene and propylene yields (C 2-3 ＝ ) Is obviously prominent and reaches 70 to 80 percent, and C of comparative example 1 and comparative example 2 2-3 ＝ The yield is less than 70 percent; in addition, the sum of the ethylene yield, propylene yield and butene yield of examples 1-4 was also higher, reaching 78% -86%, significantly higher than 74% of comparative example 1 and 73% of comparative example 2, as compared to comparative examples 1 and 2.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The preparation method of the methanol conversion catalyst taking magnesia-alumina 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 magnesia-alumina spinel;
mixing the intermediate carrier with sulfuric acid, a silicon source, a seed crystal, a template agent and water, aging and crystallizing, and performing solid-liquid separation, washing, drying and roasting on the obtained crystallized product to obtain a methanol conversion catalyst taking magnesia-alumina spinel as a carrier;
wherein the mol ratio of the sulfuric acid to the magnesia-alumina spinel is 0.01-5: 1, a step of; the molar ratio between the silicon source and the magnesia-alumina spinel is 1-50 based on silicon dioxide: 1, a step of; the molar ratio between the silicon source and the template, water and seed, calculated as silica, is 1:0.01 to 20: 10-500: 0.01 to 50; the mass ratio of the magnesia-alumina spinel, the binder and the molecular sieve is 20-40: 15-27: 30-40.
2. The method according to claim 1, wherein the magnesium source is at least one selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium carbonate and magnesium oxide;
the aluminum source is at least one selected from sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate and pseudo-boehmite;
the adhesive is at least one selected from silica sol, alumina sol, silica-alumina gel and phosphor-alumina gel;
the molecular sieve is at least one selected from silicon-aluminum molecular sieves.
3. The production method according to claim 1, wherein a molar ratio between magnesium element in the magnesium source and aluminum element in the aluminum source is 1:2 to 8.
4. The method of claim 1, wherein the silicon source is selected from one or more of silica sol, ethyl orthosilicate, 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.
5. The method of claim 1 or 4, wherein the seed crystals are selected from the group consisting of seeds of a silica-alumina molecular sieve.
6. The method of claim 1 or 4, wherein the molar ratio between the silicon source and the templating agent, water and seed, calculated as silica, is 1:0.1 to 5: 20-40: 10 to 50 percent.
7. The process according to any one of claims 1 to 6, wherein the intermediate carrier is mixed with sulfuric acid, a silicon source, a seed crystal, a template agent and water, 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.
8. A methanol conversion catalyst supported on magnesium aluminate spinel, characterized in that it is prepared by the preparation method according to any one of claims 1-7.
9. The use of the methanol conversion catalyst with magnesia-alumina spinel as a carrier in preparing low-carbon olefin by methanol conversion as claimed in claim 8.
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 CN112387267A (en) | 2021-02-23 |
| CN112387267B true 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1209121A1 (en) * | 2000-11-22 | 2002-05-29 | Haldor Topsoe A/S | Process for the catalytic oxidation of carbon monoxide and/or methanol |
-
2019
- 2019-08-13 CN CN201910743136.4A patent/CN112387267B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 镁铝尖晶石催化剂载体的制备及表征;张超武等;《陕西科技大学学报(自然科学版)》;20161225;第34卷(第06期);42-46、58 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112387267A (en) | 2021-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927213A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN106345514A (en) | Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof | |
| TW200304427A (en) | High silica chabazite, its synthesis and its use in the conversion of oxygenates to olefins | |
| US20140018592A1 (en) | Molded catalyst for the conversion of methanol to aromatics and process for producing the same | |
| CN109513457B (en) | Molecular sieve catalyst with modified magnesium aluminate spinel as carrier and preparation method thereof | |
| CN103878015B (en) | For the molecular sieve catalyst and preparation method thereof of preparing propylene from methanol | |
| US20070032379A1 (en) | Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst | |
| CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
| CN101554592A (en) | Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst | |
| JP4823655B2 (en) | Method for producing xylenes | |
| CN101684059A (en) | Method for producing propylene and ethylene through catalytic cracking of olefins | |
| US3523092A (en) | Method of preparing supported crystalline alumino-silicate zeolites | |
| CN108569707B (en) | Multi-stage pore SAPO-34 molecular sieve and application thereof in methanol-to-olefin reaction | |
| CN107954436A (en) | The preparation method of composite molecular screen | |
| 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 | |
| WO2014093467A1 (en) | Conversion of methane to aromatic compounds using a catalytic composite | |
| CN111111764A (en) | Catalyst system and use thereof | |
| RU2004120548A (en) | HYDROCARBON STEAM CRACKING CATALYST FOR PRODUCING OLEFINS, METHOD FOR ITS PREPARATION AND METHOD FOR PRODUCING OLEFINS USING THIS CATALYST | |
| CN113117729B (en) | Isomerization catalyst and method for preparing same | |
| CN113751057A (en) | Preparation and application of Silicalite-1 and silica-coated ZSM-5 catalyst | |
| CN107954435A (en) | The preparation method and its usage of composite molecular screen | |
| CN102373069A (en) | Method used for C6-alkane cracking | |
| KR102023246B1 (en) | Method for selectively enhancing yield of C4-C6 olefin and paraffin in MTO reaction using FER zeolite catalyst with cerium oxide | |
| CN102513146B (en) | Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof |
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 |