CN103537315B - 甲醇制芳烃催化剂及其制备方法 - Google Patents
甲醇制芳烃催化剂及其制备方法 Download PDFInfo
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- CN103537315B CN103537315B CN201210240007.1A CN201210240007A CN103537315B CN 103537315 B CN103537315 B CN 103537315B CN 201210240007 A CN201210240007 A CN 201210240007A CN 103537315 B CN103537315 B CN 103537315B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 77
- -1 Methanol arenes Chemical class 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 241001120493 Arene Species 0.000 title claims abstract description 21
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- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
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- 241000894007 species Species 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-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
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 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 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 19
- 238000007493 shaping process Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 abstract 1
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
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- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 206010001606 Alcohol problem Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101100129406 Neurospora africana MTA-1 gene Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 208000028505 alcohol-related disease Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—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 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种甲醇制芳烃催化剂及其制备方法，主要解决甲醇制芳烃过程中反应活性低、BTX(苯、甲苯和二甲苯)收率低的问题。本发明通过采用先制备大比表面的含芳构化活性组分的无定形硅铝氧化物，然后将其成型，最后通过气相晶化技术生成无粘结剂ZSM-5沸石制成催化剂的技术方案，较好地解决了该问题，可用于甲醇制芳烃的工业生产中。
Description
技术领域
本发明涉及一种甲醇制芳烃催化剂及其制备方法。
背景技术
芳烃，特别是轻质芳烃BTX(苯、甲苯、二甲苯)是重要的基础有机化工材料，其产量和规模仅次于乙烯和丙烯，其衍生物广泛地应用于化纤、塑料和橡胶等化工产品和精细化学品的生产中。近年来，随着石油化工及纺织工业的不断发展，芳烃的需求量不断增长。当前BTX的主要来源为催化重整和裂解汽油副产，而这两者都以石油作为最初的生产原料。据统计，我国以石油路线生产的芳烃占芳烃总产量的85%以上，国外以石油为原料生产的芳烃更是占其总产量的98%以上。随着世界原油的不断消耗和国际油价的不断上涨，芳烃产能受到抑制，生产成本大幅攀升。在我国，目前的石油产量已经无法满足经济发展的需求，对外原油依存度已经超过50%，据工信部统计2011年上半年，我国的原油对外依存度已经达到了55.3%的新高。为此，寻找一种能够代替石油化工生产芳烃的新技术对于我国化工企业提高经济效益与保障国家的能源安全具有重要的战略意义。
而甲醇通过芳构化生产芳烃就是一条非常有前景的芳烃生产路线。这一方面是因为我国煤炭资源储量丰富，以煤炭为原料生产甲醇的技术已经非常成熟，因而甲醇的产量和价格容易满足生产芳烃的需求；另一方面，甲醇产能过剩问题较严重，发展甲醇制芳烃技术则有利于缓解此问题，有效延长煤化工产业链，提高煤炭资源的利用效率。
常见的甲醇制芳烃催化剂都是采用ZSM-5分子筛为酸性载体，并采用粘结剂成型，然后负载一定量的脱氢金属组分制得。
中国专利CN1880288A介绍了一种甲醇转化制芳烃的工艺及催化剂，该工艺以小晶粒ZSM-5沸石为载体，采用与粘结剂(拟薄水铝石、γ-氧化铝或硅藻土)混合后挤压成型，最后负载活性组分镓和镧制备成催化剂，在操作压力0.1～5.0MPa、操作温度300～460oC、原料液体空速为0.1～6.0h-1条件下，反应产物经过冷却分离，液相选择性大于33%，液相中芳烃的收率大于60%。
CN101244969A报道了一种连续芳构化与催化剂再生的装置及方法。包括C1-C2烃类或甲醇芳构化及催化剂再生的流化床装置，以及适合于流化床操作的芳构化催化剂及操作方法。其所用的催化剂也是由三部分组成，分别是分子筛、金属和结构稳定剂或增强剂(即相当于粘结剂)。其中分子筛占催化剂重量的50%～70%，金属占1%～10%，其余则为粘结剂。在反应温度350～380oC，芳烃收率大于70%，BTX选择性大于55%。
综上所述，对于工业应用催化剂，一般都需要经过成型技术将催化剂制成某种形状，从而获得一定的机械强度。比如固定床所用催化剂，常采用挤条的方式制成圆柱状、三叶草状或者其它一些异形催化剂；流化床催化剂则需要添加粘结剂并喷雾成型。但是不管催化剂是何种形状，都需要达到一个共同的标准，即催化剂具有一定的机械强度，一般来说，工业上所用固定床催化剂的压碎强度要在30N/cm以上。对于分子筛，未经处理之前是粉末状态，完全没有机械强度，不适合工业应用。而催化剂要获得机械强度可以有以下两种方法：一是压片成型；二是粘结剂成型。由于工业上所用催化剂的量较大，采用压片技术显然不适用，因此添加粘结剂成型的技术成为目前常用的催化剂成型方法。
但是加入粘结剂会产生新的问题，那就是粘结剂会覆盖分子筛的部分有效表面积，从而降低反应物和反应产物在催化剂上的扩散性能。而采用无粘结剂催化剂则可以同时解决分子筛没有机械强度和粘结剂引入导致催化剂有效表面积减少和扩散限制的问题。
所谓的无粘结剂催化剂一般指催化剂中没有粘结剂或者粘结剂含量小于5%的催化剂。龙英才将ZSM-5型疏水硅沸石粉体与含二氧化硅的粘结剂混合成型干燥后，于有机胺或有机季铵碱水溶液或蒸汽中，经过晶化处理、焙烧制得一种无粘结剂ZSM-5型疏水硅沸石[龙英才一种无粘结剂疏水硅沸石吸附剂及其制备ZL94112035.X]。滕加伟等人[CN100408476C]将含量为5～50重量%的粘结剂氧化硅与ZSM型分子筛原粉形成混合物，在含有卤化有机胺和烷基二胺的水溶液或蒸汽中，经水热处理转化为一体化ZSM型分子筛，即无粘结剂分子筛。王德举等人[CN1915820A]则采用硅藻土或白炭黑为主要原料，加入晶种导向剂，并以硅溶胶或硅酸钠作为粘结剂，然后用有机胺和水蒸气气固相处理，转化为一体化小晶粒ZSM-5分子筛。
发明内容
本发明所要解决的技术问题之一是甲醇制芳烃的过程中反应活性低、BTX(苯、甲苯和二甲苯)收率低的问题，提供一种甲醇制芳烃催化剂。该催化剂具有反应活性高、BTX收率高的优点。本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的甲醇制芳烃催化剂的制备方法。
为解决上述技术问题之一，本发明采用的技术方案如下：一种甲醇制芳烃催化剂，以重量份数计，包括以下组分：
a)70～95份选自无粘结剂ZSM-5沸石；
b)1～30份选自Ag、Zn或Ga中的至少一种氧化物；
c)0～5份选自Mo、Cu、La、P、Ce或Co中的至少一种氧化物；
其中，在形成无粘结剂ZSM-5沸石的前驱体中加入组分b和组分c，即在制备无定性硅铝物种的过程中，将组分b和组分c加入其中。无粘结剂ZSM-5沸石的比表面为400～550m2/g，催化剂的径向压碎强度大于40N/cm。
上述技术方案中，催化剂的径向压碎强度优选方案为大于60N/cm。所述无粘结剂ZSM-5沸石的Si/Al原子比优选范围为10～100。
为解决上述技术问题之二，本发明采用的技术方案如下：一种甲醇制芳烃催化剂的制备方法，包括以下步骤：
1)将所需量的模板剂Ⅰ、酸催化剂、硅源、铝源、水和元素M和N的可溶性酸或者盐，在0～60℃混合均匀得到混合物Ⅰ，搅拌条件下水解0.1～10h，然后将其转入密闭容器，30℃～90℃条件下反应生成凝胶，凝胶老化后将其取出，经过干燥得到样品A，其中，模板剂Ⅰ选自聚乙二醇、聚环氧乙烷、聚氧乙烯-聚氧丙烯-聚氧乙烯(P123)或十六烷基三甲基溴化铵(CTAB)中的至少一种，酸催化剂选自盐酸、硝酸或硫酸中的至少一种；硅源选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)或正硅酸丙酯(TPOS)中的至少一种；铝源选自硝酸铝、氯化铝或硫酸铝中的至少一种，元素M选自Ag、Zn或Ga中的至少一种，元素N选自Mo、Cu、La、P、Ce或Co中的至少一种；混合物Ⅰ中各物种的质量比为：模板剂Ⅰ:SiO2=0.5～1.8：1，H+:SiO2=0.005～0.02:1，Al2O3:SiO2=0.005～0.05:1，H2O:SiO2=5～8:1，芳构化活性金属氧化物:SiO2=0.005-0.3:1，元素M的氧化物：SiO2=0.005～0.15:1，元素N的氧化物：SiO2=0～0.025:1；
2)将样品A与晶种、粘结剂混合成型，经过干燥得到样品B。其中，晶种选自HZSM-5分子筛，分子筛的Si/Al原子比为10～100；粘结剂选自硅溶胶、铝溶胶、气相白炭黑、液相白炭黑或拟薄水铝石中的至少一种，样品B中各物种的质量比为：晶种:样品A=0.001～0.1:1，粘结剂:样品A=0.1～1:1；
3)将样品B置于晶化反应釜上层，下层放置模板剂Ⅱ和水，在100℃～180℃自生压力条件下晶化0.5d～4d，随后经过水洗、60～130℃干燥2-24h、450～650℃焙烧1～8h制得甲醇制芳烃催化剂，其中，模板剂Ⅱ选自四丙基氢氧化铵、乙二胺、三乙胺、正丙胺、正丁胺或己二胺中的一种；各物种的质量比为：模板剂Ⅱ：样品B=0.001～4:1，水：样品B=1:100:1。
所谓的无粘结剂催化剂一般指催化剂中没有粘结剂或者粘结剂含量小于5%的催化剂。本发明通过在制备大比表面的无定形硅铝氧化物前驱体的过程中就引入甲醇芳构化的活性组分，然后将该前驱体与粘结剂混合成型，最后通过气相晶化技术生成无粘结剂ZSM-5沸石制成催化剂。本发明提供的无粘结剂ZSM-5沸石催化剂是一种整体型的无粘结剂型催化剂，而不是核壳结构的无粘结剂型催化剂。由于采用了具有较大比表面的硅铝氧化物前躯体，使得成型的催化剂前驱体就已经具有较大的比表面，再加上气相晶化形成了大量ZSM-5沸石所含有的微孔比表面，使得整个催化剂具有非常大的比表面，利于反应物和产物在催化剂上的扩散，提高反应活性，在相同分子筛硅铝比及相同的芳构化活性组分负载量条件下，本发明提供的催化剂比常规的粘结剂型催化剂具有更高的反应活性，产物中芳烃收率和BTX收率有8%以上的提升。同时，本发明提供的催化剂制备方法省略了晶化之后铵交换以及单独负载芳构化活性组分的步骤，减少了多次干燥、焙烧过程，降低了催化剂制备过程中的能耗，取得了较好的技术效果。
下面通过实施例对本发明作进一步阐述。但本发明并不仅限于这些实施例。
具体实施方式
【实施例1】
1)称取4g聚乙二醇、12gP123、32g浓度为1mol/L的盐酸溶液、4g硝酸铝、56g正硅酸乙酯、4.3g硝酸锌和50g水混合均匀，常温条件下强烈搅拌2h，然后将其转入密闭容器，65℃条件下使其凝胶并老化24h，随后取出凝胶，经过干燥得到样品A1。
2)取20g样品A1，1.0g晶种HZSM-5分子筛(SiO2/Al2O3比=25)，20g硅溶胶，0.5g田菁粉，捏合均匀后采用挤条的方式成型，并经过干燥得到样品B1.
3)取10g样品B1置于反应釜上层，下层放置10g水和2.0g三乙胺，在150℃自生压力条件下晶化70h，随后取出样品，经过水洗、120℃干燥12h，550℃焙烧5h得到甲醇制芳烃催化剂MTA-1。
【实施例2～9】
按照实施例1的方法，分别用硝酸银、硝酸镓、硝酸锌+硝酸钼、硝酸锌+硝酸铜、硝酸锌+硝酸镧、硝酸锌+磷酸、硝酸锌+硝酸亚铈、硝酸银+硝酸钴替代硝酸锌，制得甲醇制芳烃催化剂MTA-2、MTA-3、MTA-4、MTA-5、MTA-6、MTA-7、MTA-8、MTA-9，各组分含量列于表1。
【实施例10】
1)称取15.6g聚环氧乙烷、12gP123、117g浓度为1mol/L的盐酸溶液、5.2g硫酸铝、52.9g正硅酸甲酯、5.0g硝酸锌和110g水相混合，在搅拌条件下溶解均匀，并超声水解10分钟。随后将其转入密闭容器，在60℃条件下凝胶老化36h，随后取出凝胶，经过干燥得到样品A2。
2)称取20g样品A2、2gHZSM-5(SiO2/Al2O3比=50)分子筛、6g气相白炭黑、1g拟薄水铝石、5.5g硅溶胶(SiO2质量含量40%)、16g浓度为1.5%的稀硝酸溶液，捏合均匀后采用挤条的方式成型，经过干燥得到样品B2。
3)取10g样品B2置于反应釜上层，下层放置5g水和2.0g己二胺，在170℃自生压力条件下晶化40h，随后取出样品，经过水洗、130℃干燥8h、600℃焙烧3h得到甲醇制芳烃催化剂MTA-10。
【实施例11】
1)称取4gP123、35g正硅酸丙酯、0.84gAlCl3 .6H2O、2.0g硝酸锌、24g浓度为1mol/L的硫酸及25g水相混合，冰水浴条件下溶解均匀，并搅拌水解6h。随后将其转入密闭容器，80℃条件下使其凝胶并老化8h，取出后经过干燥得到样品A3。
2)称取20.0g样品A3、0.4gHZSM-5(SiO2/Al2O3比=100)分子筛、2.0g拟薄水铝石、10g稀硝酸(质量浓度为1.5%)、0.2g可溶性淀粉，捏合均匀后成型，经过干燥得样品B3
3)取10g样品B3置于晶化反应釜的上层，下层放置10g水、3.0g正丁胺，在自生压力条件下于130℃晶化96h，随后取出样品，经过水洗、110℃干燥18h、550焙烧4h得到甲醇制芳烃催化剂MTA-11。
【实施例12】
1)称取2gCTAB、2gP123、19.5g正硅酸甲酯、0.48g硝酸铝、1.5g硝酸锌、16g浓度为1mol/L的盐酸溶液及18g水相混合，常温搅拌下溶解，并继续水解4h后转入密闭容器，70℃条件下使其凝胶并老化24h，取出后经过干燥得样品A4。
2)取20g样品A4，1.0gHZSM-5(SiO2/Al2O3比=200)分子筛、10g硅溶胶(SiO2含量40%)、0.3g田菁粉，捏合均匀后成型，经过干燥得到样品B4。
3)取10g样品B6置于晶化反应釜的上层，下层放置6.0g水和1.5gTPAOH，在自生压力条件下与150℃晶化36h，随后取出样品，经过水洗、80℃干燥20h、500℃焙烧6h后得到甲醇制芳烃催化剂MTA-12。
【对比例1】
1)称取3.5g乙二胺、45g硅溶胶(SiO2质量含量40%)、1.0g偏铝酸钠、3.0g氢氧化钠130g水混合均匀，随后转入不锈钢晶化反应釜，于150℃自生压力条件下晶化70h，随后取出，产物经过洗涤、干燥得到样品A5。
2)取20g样品A5、7g拟薄水铝石、0.5g田菁粉、10g稀硝酸溶液(质量浓度1.5%)，捏合均匀后采用挤条的方式成型，并经过干燥、焙烧得到样品B5。
3)取20g样品B5，加入到100g质量浓度为5%的硝酸铵溶液中，于90℃条件下加热回流2h，随后将样品洗涤。重复上述步骤3次后，将样品干燥、焙烧得到样品C5。
4)取10g样品C5，加入到8g硝酸锌溶液(锌的质量浓度为7.5%)中，随后经过130℃干燥8h、600℃焙烧3h制得甲醇制芳烃催化剂MTA-13。
【对比例2】
1)称取3.0g四丙基溴化铵、50g硅溶胶(SiO2质量含量40%)、1.0g硫酸铝、3.0g氢氧化钠、3.0g氯化钠与110g水混合均匀，随后转入不锈钢晶化反应釜，于170℃自生压力条件下晶化48h，随后取出，产物经过洗涤、干燥得到样品A6。
2)取20g样品A6、20g硅溶胶，0.5g田菁粉，捏合均匀后采用挤条的方式成型，并经过干燥、焙烧得到样品B6。
3)取20g样品B6，加入到60g质量浓度为8%的氯化铵溶液中，于90℃条件下加热回流3h，随后将样品洗涤。重复上述步骤2次后，将样品干燥、焙烧得到样品C6。
4)取10g样品C6，加入到8g硝酸锌溶液(锌的质量浓度为5.0%)中，随后经过20℃干燥12h，550℃焙烧5h制得甲醇制芳烃催化剂MTA-14。
各催化剂在反应温度430℃，常压，质量空速=2.0h-1，常压的反应条件下，甲醇芳构化反应结果列于表1。
表1 甲醇芳构化结果
Claims (5)
1.一种甲醇制芳烃催化剂，以重量份数计包括以下组分：
a)70～95份选自无粘结剂ZSM-5沸石；
b)1～30份选自Ag、Zn或Ga中的至少一种氧化物；
c)0～5份选自Mo、Cu、La、P、Ce或Co中的至少一种氧化物；
其中，在制备无粘结剂ZSM-5沸石的前驱体中加入组分b和组分c，催化剂的比表面为400～550m2/g，催化剂的径向压碎强度大于40N/cm；
所述催化剂采用的制备方法，包括以下步骤：
1)将所需量的模板剂Ⅰ、酸催化剂、硅源、铝源、水和元素M和N的可溶性酸或者盐，在0～60℃混合均匀得到混合物Ⅰ，搅拌条件下水解0.1～10h，然后将其转入密闭容器，30℃～90℃条件下反应生成凝胶，凝胶老化后将其取出，经过干燥得到样品A，其中，模板剂Ⅰ选自聚乙二醇、聚环氧乙烷、聚氧乙烯-聚氧丙烯-聚氧乙烯或十六烷基三甲基溴化铵(CTAB)中的至少一种，酸催化剂选自盐酸、硝酸或硫酸中的至少一种；硅源选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)或正硅酸丙酯(TPOS)中的至少一种；铝源选自硝酸铝、氯化铝或硫酸铝中的至少一种，元素M选自Ag、Zn或Ga中的至少一种，元素N选自Mo、Cu、La、P、Ce或Co中的至少一种；混合物Ⅰ中各物种的质量比为：模板剂Ⅰ:SiO2＝0.5～1.8：1，H+:SiO2＝0.005～0.02:1，Al2O3:SiO2＝0.005～0.05:1，H2O:SiO2＝5～8:1，芳构化活性金属氧化物:SiO2＝0.005-0.3:1，元素M的氧化物：SiO2＝0.005～0.15:1，元素N的氧化物：SiO2＝0～0.025:1；
2)将样品A与晶种、粘结剂混合成型，经过干燥得到样品B；其中，晶种选自HZSM-5分子筛，分子筛的Si/Al原子比为10～100；粘结剂选自硅溶胶、铝溶胶、气相白炭黑、液相白炭黑或拟薄水铝石中的至少一种，样品B中各物种的质量比为：晶种:样品A＝0.001～0.1:1，粘结剂:样品A＝0.1～1:1；
3)将样品B置于晶化反应釜上层，下层放置模板剂Ⅱ和水，在100℃～180℃自生压力条件下晶化0.5d～4d，随后经过水洗、60～130℃干燥2-24h、450～650℃焙烧1～8h制得甲醇制芳烃催化剂，其中，模板剂Ⅱ选自四丙基氢氧化铵、乙二胺、三乙胺、正丙胺、正丁胺或己二胺中的一种；各物种的质量比为：模板剂Ⅱ：样品B＝0.001～4:1，水：样品B＝1:100:1。
2.根据权利要求1所述的催化剂，其特征在于催化剂的径向压碎强度大于60N/cm。
3.根据权利要求1所述的催化剂，其特征在于所述无粘结剂ZSM-5沸石的Si/Al原子比为10～100。
4.权利要求1所述甲醇制芳烃催化剂的制备方法，包括以下步骤：
1)将所需量的模板剂Ⅰ、酸催化剂、硅源、铝源、水和元素M和N的可溶性酸或者盐，在0～60℃混合均匀得到混合物Ⅰ，搅拌条件下水解0.1～10h，然后将其转入密闭容器，30℃～90℃条件下反应生成凝胶，凝胶老化后将其取出，经过干燥得到样品A，其中，模板剂Ⅰ选自聚乙二醇、聚环氧乙烷、聚氧乙烯-聚氧丙烯-聚氧乙烯或十六烷基三甲基溴化铵(CTAB)中的至少一种，酸催化剂选自盐酸、硝酸或硫酸中的至少一种；硅源选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)或正硅酸丙酯(TPOS)中的至少一种；铝源选自硝酸铝、氯化铝或硫酸铝中的至少一种，元素M选自Ag、Zn或Ga中的至少一种，元素N选自Mo、Cu、La、P、Ce或Co中的至少一种；混合物Ⅰ中各物种的质量比为：模板剂Ⅰ:SiO2＝0.5～1.8：1，H+:SiO2＝0.005～0.02:1，Al2O3:SiO2＝0.005～0.05:1，H2O:SiO2＝5～8:1，芳构化活性金属氧化物:SiO2＝0.005-0.3:1，元素M的氧化物：SiO2＝0.005～0.15:1，元素N的氧化物：SiO2＝0～0.025:1；
2)将样品A与晶种、粘结剂混合成型，经过干燥得到样品B；其中，晶种选自HZSM-5分子筛，分子筛的Si/Al原子比为10～100；粘结剂选自硅溶胶、铝溶胶、气相白炭黑、液相白炭黑或拟薄水铝石中的至少一种，样品B中各物种的质量比为：晶种:样品A＝0.001～0.1:1，粘结剂:样品A＝0.1～1:1；
3)将样品B置于晶化反应釜上层，下层放置模板剂Ⅱ和水，在100℃～180℃自生压力条件下晶化0.5d～4d，随后经过水洗、60～130℃干燥2-24h、450～650℃焙烧1～8h制得甲醇制芳烃催化剂，其中，模板剂Ⅱ选自四丙基氢氧化铵、乙二胺、三乙胺、正丙胺、正丁胺或己二胺中的一种；各物种的质量比为：模板剂Ⅱ：样品B＝0.001～4:1，水：样品B＝1:100:1。
5.根据权利要求4所述的制备方法，其特征在于所述的聚氧乙烯-聚氧丙烯-聚氧乙烯为P123。
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Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9783460B2 (en) | 2013-12-20 | 2017-10-10 | Exxonmobil Chemical Patents Inc. | Process for converting oxygenates to aromatic hydrocarbons |
| WO2015094687A1 (en) | 2013-12-20 | 2015-06-25 | Exxonmobil Research And Engineering Company | Bound catalyst for selective conversion of oxygenates to aromatics |
| RU2544017C1 (ru) | 2014-01-28 | 2015-03-10 | Ольга Васильевна Малова | Катализатор и способ ароматизации с3-с4 газов, легких углеводородных фракций алифатических спиртов, а также их смесей |
| RU2544241C1 (ru) | 2014-01-22 | 2015-03-20 | Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" | Способ получения ароматических углеводородов из природного газа и установка для его осуществления |
| RU2550354C1 (ru) | 2014-03-28 | 2015-05-10 | Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" | Способ получения концентрата ароматических углеводородов из легких алифатических углеводородов и установка для его осуществления |
| RU2558955C1 (ru) | 2014-08-12 | 2015-08-10 | Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" | Способ получения концентрата ароматических углеводородов из жидких углеводородных фракций и установка для его осуществления |
| CN104801332B (zh) * | 2014-01-24 | 2017-12-19 | 上海碧科清洁能源技术有限公司 | 一种甲醇制芳烃过程催化剂制备方法 |
| CN104152175B (zh) * | 2014-07-30 | 2016-04-20 | 浙江大学 | 一种由生物油馏分制备芳香烃的方法 |
| CN104437601B (zh) * | 2014-12-15 | 2019-08-16 | 北京惠尔三吉绿色化学科技有限公司 | 一种用于甲醇制丙烯的改性zsm-5分子筛催化剂及其应用 |
| CN104841473A (zh) * | 2015-04-21 | 2015-08-19 | 东南大学 | 一种醇类芳构化催化剂的制备方法 |
| CN105148979B (zh) * | 2015-09-21 | 2017-06-30 | 西南化工研究设计院有限公司 | 一种用于丙烷脱氢转化制丙烯复合载体催化剂及其制备方法 |
| CN105195213B (zh) * | 2015-10-12 | 2017-09-26 | 华电煤业集团有限公司 | 一种甲醇/二甲醚转化制芳烃的催化剂的原位合成方法 |
| CN106607080B (zh) * | 2015-10-21 | 2019-01-18 | 上海碧科清洁能源技术有限公司 | 一种用于以甲醇为原料制备芳烃的催化剂及其制备和应用方法 |
| CN105435839B (zh) * | 2015-12-07 | 2018-02-16 | 中国海洋石油总公司 | 一种含两种分子筛的甲醇制芳烃催化剂及制备方法 |
| CN105498829B (zh) * | 2015-12-10 | 2018-06-26 | 大唐国际化工技术研究院有限公司 | 一种甲醇芳构化催化剂及其制备方法和应用 |
| WO2017155424A1 (en) | 2016-03-09 | 2017-09-14 | Limited Liability Company "New Gas Technologies-Synthesis" (Llc "Ngt-Synthesis") | Method and plant for producing high-octane gasolines |
| WO2017187873A1 (ja) * | 2016-04-28 | 2017-11-02 | 旭化成株式会社 | 芳香族炭化水素含有化合物の製造方法 |
| WO2018007485A1 (en) * | 2016-07-08 | 2018-01-11 | Haldor Topsøe A/S | Natural gas based mta |
| WO2018007487A1 (en) * | 2016-07-08 | 2018-01-11 | Haldor Topsøe A/S | Optimizing a mta process |
| CN109477002A (zh) * | 2016-07-28 | 2019-03-15 | 国际壳牌研究有限公司 | 从固体生物质生产富含芳香烃的高级烃 |
| CN106866328B (zh) * | 2017-01-16 | 2019-12-10 | 厦门大学 | 一种甲醇高选择性制芳烃的方法 |
| CN108786905B (zh) * | 2017-04-27 | 2020-09-15 | 中国科学院大连化学物理研究所 | 一种苯、甲醇烷基化制甲苯联产对二甲苯的催化剂的原位制备方法 |
| CN111111752B (zh) * | 2018-10-30 | 2022-09-06 | 中国石油化工股份有限公司 | 无粘结剂整体式催化剂、制备方法及其用途 |
| CN109908949A (zh) * | 2019-03-25 | 2019-06-21 | 北京化工大学 | 一种双金属改性纳米hzsm-5分子筛催化剂、其制备方法及用途 |
| CN112619686B (zh) * | 2019-10-09 | 2024-01-30 | 中国石油化工股份有限公司 | 负载型非贵金属脱氢催化剂及其制备方法和应用 |
| CN112657498A (zh) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | 甲醇制芳烃的催化剂及其制备方法 |
| CN111233798A (zh) * | 2020-02-28 | 2020-06-05 | 浙江糖能科技有限公司 | 双-（5-甲酰基糠基）醚的制备方法、聚酰胺类材料 |
| CN111530496A (zh) * | 2020-06-01 | 2020-08-14 | 宁夏大学 | 一种制备芳烃的方法 |
| CN112044466A (zh) * | 2020-07-29 | 2020-12-08 | 华东理工大学 | 一种mtp副产品芳构化制取高值芳烃的方法 |
| CN113441171A (zh) * | 2021-05-12 | 2021-09-28 | 中新国际联合研究院 | 一种载体改性的银基乙烯脱除剂及其制备方法和应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927714A (zh) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | 无粘结剂zsm型分子筛的制备方法 |
| CN101550051A (zh) * | 2009-04-23 | 2009-10-07 | 天脊煤化工集团股份有限公司 | 一种提高甲醇芳构化制取芳烃选择性的工艺及其催化剂的制备方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894104A (en) * | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Aromatization of hetero-atom substituted hydrocarbons |
| CS191916B2 (en) * | 1973-08-09 | 1979-07-31 | Mobil Oil Corp | Method of producing aromatic hydrocarbons |
| US4686312A (en) | 1981-12-23 | 1987-08-11 | Mobil Oil Corporation | Aromatics production |
| US4621161A (en) * | 1984-01-23 | 1986-11-04 | Mobil Oil Corporation | Oxygenate conversion over activated zeolite catalyst |
| US6177374B1 (en) * | 1997-01-17 | 2001-01-23 | Council Of Scientific & Industrial Research | Catalyst comprising oxides of silicon, zinc and aluminium used for the preparation of LPG and high octane aromatics and a process for preparing the same |
| US6372680B1 (en) | 1999-07-27 | 2002-04-16 | Phillips Petroleum Company | Catalyst system for converting oxygenated hydrocarbons to aromatics |
| US6372949B1 (en) * | 1999-10-15 | 2002-04-16 | Mobil Oil Corporation | Single stage process for converting oxygenates to gasoline and distillate in the presence of undimensional ten member ring zeolite |
| US6926882B2 (en) * | 2000-01-05 | 2005-08-09 | Exxonmobil Chemical Patents Inc. | Porous inorganic macrostructure materials and process for their preparation |
| RU2186089C1 (ru) * | 2001-02-12 | 2002-07-27 | Научно-инженерный центр "Цеосит" Объединенного института катализа СО РАН | Способ получения высокооктановых бензиновых фракций и ароматических углеводородов |
| CN100548945C (zh) | 2006-05-12 | 2009-10-14 | 中国科学院山西煤炭化学研究所 | 甲醇转化制芳烃工艺及催化剂和催化剂制备方法 |
| EP2183203A1 (en) | 2007-08-13 | 2010-05-12 | Saudi Basic Industries Corporation | Process for converting aliphatic oxygenates to aromatics |
| CN101244969B (zh) | 2008-03-25 | 2012-05-23 | 清华大学 | 一种连续芳构化与催化剂再生的装置及其方法 |
-
2012
- 2012-07-12 CN CN201210240007.1A patent/CN103537315B/zh active Active
-
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- 2013-07-11 ZA ZA2013/05248A patent/ZA201305248B/en unknown
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- 2013-07-12 BR BR102013017946-9A patent/BR102013017946B1/pt active IP Right Grant
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927714A (zh) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | 无粘结剂zsm型分子筛的制备方法 |
| CN101550051A (zh) * | 2009-04-23 | 2009-10-07 | 天脊煤化工集团股份有限公司 | 一种提高甲醇芳构化制取芳烃选择性的工艺及其催化剂的制备方法 |
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| Publication number | Publication date |
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| RU2013132371A (ru) | 2015-01-20 |
| BR102013017946B1 (pt) | 2019-11-05 |
| CN103537315A (zh) | 2014-01-29 |
| SA113340714B1 (ar) | 2015-10-05 |
| US20140018592A1 (en) | 2014-01-16 |
| AU2013206818A1 (en) | 2014-01-30 |
| AU2013206818B2 (en) | 2017-02-23 |
| US9339801B2 (en) | 2016-05-17 |
| BR102013017946A2 (pt) | 2015-09-01 |
| RU2607633C2 (ru) | 2017-01-10 |
| ZA201305248B (en) | 2014-03-26 |
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