CN115318343A - Preparation method and application of fluidized catalyst for preparing styrene by toluene side chain alkylation - Google Patents
Preparation method and application of fluidized catalyst for preparing styrene by toluene side chain alkylation Download PDFInfo
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- CN115318343A CN115318343A CN202111544874.XA CN202111544874A CN115318343A CN 115318343 A CN115318343 A CN 115318343A CN 202111544874 A CN202111544874 A CN 202111544874A CN 115318343 A CN115318343 A CN 115318343A
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- raw material
- catalyst
- weight
- molecular sieve
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 24
- 230000029936 alkylation Effects 0.000 title claims abstract description 21
- 125000003944 tolyl group Chemical group 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000001694 spray drying Methods 0.000 claims abstract description 21
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 29
- 239000002808 molecular sieve Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 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 27
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- 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 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- 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 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 4
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001417 caesium ion Inorganic materials 0.000 claims description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000009718 spray deposition Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HKEZNGAHGMYDHE-UHFFFAOYSA-N methanol styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1.CO HKEZNGAHGMYDHE-UHFFFAOYSA-N 0.000 description 1
- VDNCVCXESAGSIL-UHFFFAOYSA-N methanol toluene Chemical compound OC.CC1=CC=CC=C1.CC1=CC=CC=C1 VDNCVCXESAGSIL-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to a preparation method and application of a fluidized catalyst for preparing styrene by toluene side chain alkylation, belonging to the technical field of catalyst preparation and chemical engineering. The catalyst comprises a methanol dehydrogenation component and an intermediate species stabilizing component; the fluidized catalyst is prepared by spray drying for many times, avoids direct contact of various active components, has low wear index and good activity, and can be applied to a fluidized bed reaction process for preparing styrene by toluene side chain alkylation.
Description
Technical Field
The invention relates to a production method and application of a microspherical fluidized catalyst for preparing styrene by toluene side chain alkylation, belonging to the technical field of catalyst preparation and chemical engineering.
Background
Styrene is an important chemical raw material, can be used for producing various downstream products such as polystyrene, styrene butadiene rubber and the like, and the total consumption of the styrene in the world reaches 3125.3 ten thousand tons in 2020. Currently, over 80% of the styrene produced industrially is produced by the ethylbenzene dehydrogenation process, which consists of two steps, benzene and ethylene alkylation to produce ethylbenzene and ethylbenzene dehydrogenation. The process has the advantages of long process route, large equipment investment, more side reactions and high energy consumption.
Sidorenko et al (Dokl Akad Nauk SSSR [ J ],1967,173 (1): 132-134) first discovered that toluene and methanol were capable of undergoing a side-alkylation reaction on an alkali metal ionic zeolite to produce styrene in 1967. This reaction has been of great interest to both the academic and industrial world for half a century. Compared with the traditional ethylbenzene dehydrogenation process, the toluene side-chain alkylation reaction can generate styrene in one step, so that the dehydrogenation step is omitted, the energy consumption is reduced, and the cost of raw materials can be greatly reduced by taking toluene and methanol as raw materials. According to the evaluation by Exelus corporation (petrochemical economics [ J ],2007, (3): 12), the toluene methanol side chain alkylation process can reduce the raw material cost per ton of styrene by about $ 350 and the energy consumption by about $ 20 compared to the ethylbenzene dehydrogenation process.
The main active component in the current high-efficiency toluene methanol side chain alkylation catalyst is usually an alkali metal ionic molecular sieve, and the catalyst is easy to generate carbon deposition and inactivation in the reaction process and needs frequent regeneration. The fluidized bed process can realize continuous reaction-regeneration of the catalyst, and can well solve the problem that the catalyst is easy to deposit carbon and deactivate carbon. In addition, in the high-activity toluene methanol side chain alkylation catalyst, besides the alkali metal ionic molecular sieve, a methanol dehydrogenation auxiliary agent and a stabilizing auxiliary agent of an intermediate species need to be added. Research shows that in order to effectively exert the synergistic effect of the three components of the alkali metal ionic molecular sieve, the methanol dehydrogenation auxiliary and the intermediate species stabilizing auxiliary, a certain space distance needs to be kept among the three components (Applied Catalysis A: general,2020,605, 117807).
Microspherical catalysts required for fluidized beds are typically prepared by spray drying. In the process of preparing the microspherical catalyst by spray drying, the components of the catalyst need to be mixed and prepared into aqueous slurry, and in the process, active species in the methanol dehydrogenation component and the intermediate species stabilizing component are undoubtedly impregnated and loaded on the alkali metal ionic molecular sieve, so that the three active components are in direct contact with each other, and the synergistic effect is not favorably realized.
Disclosure of Invention
The invention aims to provide a preparation method and application of a microsphere fluidized catalyst in a reaction for preparing styrene by toluene side chain alkylation.
In order to realize reasonable space matching among the alkali metal ionic molecular sieve, the methanol dehydrogenation component and the intermediate species stable component in the catalyst, the alkali metal ionic molecular sieve, the methanol dehydrogenation component, the intermediate species stable component, the forming assistant and the binder are respectively prepared into the microsphere fluidized catalyst by three times of spray drying.
According to one aspect of the present invention, there is provided a process for the preparation of a methanol and toluene side chain alkylation catalyst comprising a methanol dehydrogenation component and an intermediate species stabilizing component;
the preparation method comprises the following steps:
(1) Respectively soaking the methanol dehydrogenation component and the intermediate species stable component in an aqueous solution containing a forming auxiliary agent for pretreatment, then separating and drying;
(2) Preparing an aqueous slurry a containing an alkali metal ionic molecular sieve and a binder;
(3) And (3) adding the methanol dehydrogenation component dried in the step (1) and the intermediate species stabilizing component into the aqueous slurry a in the step (2), uniformly mixing to prepare aqueous slurry b, and then carrying out spray drying to obtain the catalyst.
Optionally, the methanol dehydrogenation component is a microsphere having a particle size of less than 10 μm.
Optionally, the methanol dehydrogenation component is prepared by spray drying an aqueous material c with the solid content of 20wt% -70 wt%;
the water-containing material c contains a raw material I and a raw material II, and the mass ratio of the raw material I to the raw material II is 0.01-0.25;
the raw material I is selected from at least one of copper nitrate, silver nitrate, zinc nitrate, chromium nitrate and cerium nitrate; the raw material II is at least one selected from white carbon black, silica sol, alumina sol, sodium silicate, sodium aluminate and sodium metaaluminate.
Optionally, the intermediate species stabilising component is a microsphere having a particle size of less than 10 μm.
Optionally, the intermediate species stabilizing component is formed by spray drying an aqueous material d with a solid content of 20wt% to 70 wt%;
the water-containing material d contains a raw material III and a raw material IV, and the mass ratio of the raw material III to the raw material IV is 0.01-0.3;
the raw material III is at least one of sodium borate, potassium borate, sodium phosphate, potassium phosphate, phosphoric acid, boric acid and boron oxide; the raw material IV is selected from at least one of white carbon black, silica sol and aluminum sol or the like.
Optionally, in the step (1), after soaking, performing centrifugal separation, and drying at 40-200 ℃; the soaking time is 0.5-5 hours.
Optionally, the soaking time is 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, or any value between any two of the above.
Optionally, in the step (1), the concentration of the aqueous solution containing the forming aid is 0.05 to 1wt%;
the mass ratio of the aqueous slurry b, the alkali metal ionic molecular sieve, the methanol dehydrogenation component, the intermediate species stabilizing component to the binder is 0.5-5.
Optionally, the binder is a silicon-or aluminum-containing amorphous binder.
Preferably, the amorphous binder containing silicon or aluminum is selected from at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite, bentonite, silica sol, water glass, white carbon black, alumina sol, pseudo-boehmite, alumina, sodium aluminate and sodium metaaluminate.
Optionally, the forming aid is at least one selected from stearic acid, benzalkonium chloride palmitate, sodium dodecylbenzene sulfonate, ammonium dodecylsulfate, sodium dodecylsulfate, dodecyl phosphate, sodium pyrophosphate and octadecyl trimethyl ammonium chloride.
Optionally, the alkali metal ionic molecular sieve consists of exchanged alkali metal ions and a molecular sieve framework; the molecular sieve is at least one of an X-type molecular sieve, a Y-type molecular sieve and an L-type molecular sieve according to the skeleton topological structure type; the exchanged alkali metal ions are selected from at least one of K ions, rb ions and Cs ions.
One aspect of the present application provides a reaction for preparing styrene by toluene side chain alkylation, wherein toluene and methanol react to generate styrene under the condition of a catalyst;
the catalyst is selected from the catalyst prepared by the preparation method and one of the catalysts.
Optionally, the reaction is carried out in a fluidized bed reactor, and the catalyst is fluidized.
Optionally, the molar ratio of the toluene to the methanol is 0.1-10, and the total space velocity of the toluene to the methanol is 0.5-8 h -1 The reaction temperature is 300-500 deg.C, and the reaction pressure is 0-20 MPa (gauge pressure).
Alternatively, the reaction temperature is 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 470 ℃, 490 ℃, or any value between any of the foregoing.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly prepares the small-particle-size microspheres of the methanol dehydrogenation component and the intermediate species stable component respectively by a spray drying method, and then adds the two microspheres into slurry containing an alkali metal ion type molecular sieve for spray drying and forming again, thereby effectively solving the problem of distribution of three functional components in the formed catalyst, avoiding direct contact of various active components, preparing the high-performance catalyst for preparing the styrene by toluene side chain alkylation, which is suitable for a fluidized bed reaction process, and having low catalyst wear index and good activity.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the materials used in the examples were obtained from commercial sources, and the equipment was set to the parameters recommended by the manufacturer.
The attrition Index of the microspherical catalysts of the examples and comparative examples was determined according to the ASTM-D-5757-00 International Standard using an Air Jet Index (Air Jet Index, AJI, weight percent of catalyst carried over by attrition of the catalyst within 5 hours).
EXAMPLE 1 preparation of alkali Metal Ionic molecular sieves
Using commercially available 13X molecular sieve raw powder (Si/Al = 1.23) as a matrix, and using 0.3mol/L CsNO 3 The solution was exchanged 4 times at 80 ℃ and the solid-to-liquid ratio of the 13X molecular sieve raw powder to the cesium nitrate solution was 1. Washing with deionized water, filtering, drying at 120 ℃ overnight, and roasting in air at 550 ℃ for 5h to obtain a sample CsX.
EXAMPLE 2 preparation of microspheroidal methanol dehydrogenation component
EXAMPLE 2-1 preparation of microspheroidal methanol dehydrogenation component T-1
Dissolving 5 parts by weight of copper nitrate and 10 parts by weight of silver nitrate in 500 parts by weight of deionized water, fully dissolving, then adding 150 parts by weight of white carbon black, stirring for 20min, adding 30 parts by weight of aluminum sol (solid content is 20.1 wt%), stirring for 20min, then adding 50 parts by weight of silica sol (solid content is 28.8 wt%), pulping, colloid milling, defoaming, spray drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical methanol dehydrogenation component named as T-1.
Example 2-2 preparation of microspherical methanol dehydrogenation component T-2
Dissolving 5 parts by weight of zinc nitrate and 15 parts by weight of cerium nitrate in 500 parts by weight of deionized water, fully dissolving, then adding 130 parts by weight of white carbon black and 30 parts by weight of sodium aluminate, stirring for 20min, adding 20 parts by weight of alumina sol (solid content is 20.1 wt%), stirring for 20min, then adding 50 parts by weight of silica sol (solid content is 28.8 wt%), pulping, colloid milling, defoaming, spray drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical methanol dehydrogenation component named as T-2.
Examples 2-3 preparation of microspherical methanol dehydrogenation component T-3
Dissolving 5 parts by weight of chromium nitrate and 10 parts by weight of silver nitrate in 500 parts by weight of deionized water, fully dissolving, then adding 130 parts by weight of white carbon black and 30 parts by weight of sodium silicate, stirring for 20min, adding 20 parts by weight of alumina sol (solid content is 20.1 wt%), stirring for 20min, then adding 50 parts by weight of silica sol (solid content is 28.8 wt%), pulping, colloid milling, defoaming, spray drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain a microspherical methanol dehydrogenation component named as T-3.
EXAMPLE 3 preparation of microspheroidal intermediate species stabilising component
Example 3-1 preparation of microspheroidal intermediate species stabilising component W-1
Adding 3 parts by weight of sodium borate, 8 parts by weight of potassium phosphate and 8 parts by weight of boric acid into 500 parts by weight of deionized water, stirring for 20min, adding 150 parts by weight of white carbon black, stirring for 20min, adding 30 parts by weight of aluminum sol (solid content is 20.1 wt%), stirring for 20min, adding 60 parts by weight of silica sol (solid content is 28.8 wt%), pulping, colloid milling, defoaming, spray drying and forming, and roasting at 550 ℃ for 4 hours in an air atmosphere to obtain a microspherical intermediate species stable component named as W-1.
EXAMPLE 3-2 preparation of microspheroidal intermediate species stabilizing component W-2
Adding 3 parts by weight of potassium borate, 8 parts by weight of sodium phosphate and 7 parts by weight of boron oxide into 500 parts by weight of deionized water, stirring for 20min, adding 120 parts by weight of white carbon black, stirring for 20min, adding 20 parts by weight of aluminum sol (solid content is 20.1 wt%), stirring for 20min, adding 80 parts by weight of silica sol (solid content is 28.8 wt%), pulping, colloid milling, defoaming, spray drying and forming, and roasting at 550 ℃ for 4 hours to obtain the microspherical intermediate species stable component named as W-2.
EXAMPLE 4 preparation of microspherical catalyst for side-chain alkylation of toluene to styrene
EXAMPLE 4-1 preparation of microspherical catalyst C-1 for the alkylation of toluene side chains to styrene
Placing T-1 and W-1 in 0.5wt% benzalkonium chloride palmitate and 0.5wt% sodium dodecyl benzene sulfonate solution respectively, soaking for 2 hours at a solid-to-liquid ratio of 1.
100 parts by weight of CsX, 60 parts by weight of kaolin, 10 parts by weight of bentonite, 10 parts by weight of water glass (solid content 35 wt%), 40 parts by weight of aluminum sol (solid content 20.1 wt%) and 50 parts by weight of silica sol (solid content 28.8 wt%) are sequentially added into 500 parts by weight of deionized water to be stirred, pulped and colloid-milled. Then adding 20 parts by weight of the treated T-1 and 25 parts by weight of W-1, ultrasonically mixing uniformly, removing bubbles, spray-drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical catalyst for preparing styrene by alkylating the side chain of toluene, which is named as C-1.
EXAMPLE 4-2 preparation of catalyst C-2 for the alkylation of microspherical toluene side-chains to styrene
Placing T-2 and W-1 in 0.5wt% ammonium dodecyl sulfate and 0.5wt% sodium dodecyl sulfate solution respectively, soaking for 2 hours at a solid-to-liquid ratio of 1.
100 parts by weight of CsX, 60 parts by weight of kaolin, 10 parts by weight of attapulgite, 10 parts by weight of water glass (solid content 35 wt%), 40 parts by weight of aluminum sol (solid content 20.1 wt%) and 50 parts by weight of silica sol (solid content 28.8 wt%) are sequentially added to 500 parts by weight of deionized water to be stirred, pulped and colloid-milled. Then adding 20 parts by weight of the treated T-2 and 25 parts by weight of W-1, ultrasonically mixing uniformly, removing bubbles, spray-drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical catalyst for preparing styrene by alkylating the side chain of toluene, which is named as C-2.
EXAMPLE 4-3 preparation of microspherical catalyst C-3 for the alkylation of toluene side chains to styrene
Placing T-3 and W-1 in 0.5wt% ammonium dodecyl sulfate and 0.5wt% sodium dodecyl sulfate solution respectively, soaking for 2 hours at a solid-to-liquid ratio of 1.
100 parts by weight of CsX, 60 parts by weight of kaolin, 10 parts by weight of bentonite, 10 parts by weight of water glass (solid content 35 wt%), 40 parts by weight of aluminum sol (solid content 20.1 wt%) and 50 parts by weight of silica sol (solid content 28.8 wt%) are sequentially added into 500 parts by weight of deionized water to be stirred, pulped and colloid-milled. Then adding 20 parts by weight of the treated T-3 and 25 parts by weight of W-1, ultrasonically mixing uniformly, removing bubbles, spray-drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain a microspherical catalyst for preparing styrene by alkylating a toluene side chain, wherein the catalyst is named as C-3.
EXAMPLE 4-4 preparation of catalyst C-4 for the alkylation of microspherical toluene side-chains to styrene
Placing T-1 and W-2 in 0.5wt% benzalkonium chloride palmitate and 0.5wt% sodium dodecyl benzene sulfonate solution respectively, soaking for 2 hours at a solid-to-liquid ratio of 1.
100 parts by weight of CsX, 60 parts by weight of kaolin, 5 parts by weight of chlorite, 10 parts by weight of water glass (solid content of 35 wt%), 40 parts by weight of aluminum sol (solid content of 20.1 wt%) and 50 parts by weight of silica sol (solid content of 28.8 wt%) are sequentially added into 500 parts by weight of deionized water to be stirred, pulped and colloid-milled. Then adding 20 parts by weight of the treated T-1 and 25 parts by weight of W-2, ultrasonically mixing uniformly, removing bubbles, spray-drying and forming, and roasting for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical catalyst for preparing styrene by alkylating the side chain of toluene, which is named as C-4.
Comparative example
100 parts by weight of CsX, 0.55 part by weight of copper nitrate, 1.1 part by weight of silver nitrate, 0.4 part by weight of sodium borate, 1.1 part by weight of potassium phosphate, 1.1 part by weight of boric acid, 40 parts by weight of white carbon black, 60 parts by weight of kaolin, 10 parts by weight of bentonite, 10 parts by weight of water glass (solid content 35 wt%), 47 parts by weight of aluminum sol (solid content 20.1 wt%) and 64 parts by weight of silica sol (solid content 28.8 wt%) are sequentially added into 500 parts by weight of deionized water to be stirred, pulped, colloid-milled, defoamed, spray-dried and molded, and calcined for 4 hours at 550 ℃ in an air atmosphere to obtain the microspherical comparative catalyst.
Example 5 evaluation of catalyst reaction Performance
The reaction performance of the microspherical catalyst for preparing styrene by toluene side chain alkylation is evaluated by adopting a fixed fluidized bed. The microspherical catalysts C-1, C-2, C-3, C-4 obtained in example 4 and the microspherical comparative catalysts obtained in comparative examples were packed in a fixed fluidized bed reactor having an inner diameter of 35mm and a catalyst loading of 30g, respectively. The molar ratio of the fed toluene to the methanol is 3 -1 Pumping the mixture by a plunger pump, vaporizing the mixture by a preheating furnace and then introducing the vaporized mixture into a reactor, wherein the outlet pressure of the reactor is normal pressure, and the reaction temperature is 420 ℃.
In the reaction evaluation, the product was chromatographed using Agilent 7890A. Separating hydrocarbon components by Agilent CP-WAX 25m × 32 μm × 1.2 μm capillary column, detecting with FID detector, and detecting with CO and CO 2 And H 2 The separation is carried out by using a Porapark Q4 m multiplied by 1/8' packed column and a TCD detector.
In the evaluation of the reaction, the conversion X of toluene Toluene Methanol conversion X Methanol Styrene selectivity S Styrene (meth) acrylic acid ester Ethylbenzene selectivity S Ethylbenzene production The calculation method comprises the following steps:
the reaction results are shown in table 1.
TABLE 1 styrene reaction Performance and attrition index by toluene side chain alkylation
* The reaction was sampled and analyzed 1 time every 1 hour, and the above reaction results were average values in 5 hours.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (7)
1. A preparation method of a fluidized catalyst for preparing styrene by toluene side chain alkylation is characterized in that the catalyst comprises an alkali metal ionic molecular sieve, a methanol dehydrogenation component, an intermediate species stabilizing component and an amorphous binder containing silicon or aluminum;
the preparation method comprises the following steps:
(1) Respectively soaking the methanol dehydrogenation component and the intermediate species stable component in an aqueous solution containing a forming auxiliary agent for pretreatment, then separating and drying;
(2) Preparing an aqueous slurry a containing an alkali metal ionic molecular sieve and a binder;
(3) And (3) adding the methanol dehydrogenation component dried in the step (1) and the intermediate species stabilizing component into the aqueous slurry a obtained in the step (2), uniformly mixing to prepare aqueous slurry b, and then performing spray drying to obtain the catalyst.
2. The method of claim 1, wherein the methanol dehydrogenation component is microspheres having a particle size of less than 10 μ ι η;
preferably, the methanol dehydrogenation component is prepared by spray drying aqueous slurry c with the solid content of 20wt% -70 wt%;
the aqueous slurry c contains a raw material I and a raw material II, and the mass ratio of the raw material I to the raw material II is 0.01-0.25;
the raw material I is selected from at least one of copper nitrate, silver nitrate, zinc nitrate, chromium nitrate and cerium nitrate; the raw material II is at least one selected from white carbon black, silica sol, alumina sol, sodium silicate, sodium aluminate and sodium metaaluminate.
3. The method of claim 1, wherein the intermediate species stabilizing component is microspheres having a particle size of less than 10 μ ι η;
preferably, the intermediate species stabilizing component is formed by spray drying an aqueous slurry d with a solid content of 20wt% to 70 wt%;
the aqueous slurry d contains a raw material III and a raw material IV, and the mass ratio of the raw material III to the raw material IV is (0.01-0.3);
the raw material III is at least one of sodium borate, potassium borate, sodium phosphate, potassium phosphate, phosphoric acid, boric acid and boron oxide; the raw material IV is selected from at least one of white carbon black, silica sol and aluminum sol.
4. The method according to claim 1, wherein in the step (1), the methanol dehydrogenation component and the intermediate species stabilizing component are soaked, centrifuged, and dried at 40-200 ℃; the soaking time is 0.5 to 5 hours;
preferably, in the step (1), the concentration of the forming assistant aqueous solution is 0.05-1 wt%;
the mass ratio of the aqueous slurry b, the alkali metal ionic molecular sieve, the methanol dehydrogenation component, the intermediate species stabilizing component and the binder is 0.5-5.
5. The method of claim 1, wherein the binder is a silicon-or aluminum-containing amorphous binder;
preferably, the amorphous binder containing silicon or aluminum is selected from at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite, bentonite, silica sol, water glass, white carbon black, alumina sol, pseudo-boehmite, alumina, sodium aluminate and sodium metaaluminate;
preferably, the forming aid is at least one selected from stearic acid, benzalkonium chloride palmitate, sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate, sodium dodecyl sulfate, dodecyl phosphate, sodium pyrophosphate and octadecyl trimethyl ammonium chloride.
6. The method of claim 1, wherein the alkali metal ionic molecular sieve is comprised of exchanged alkali metal ions with a molecular sieve framework; the molecular sieve is at least one of an X-type molecular sieve, a Y-type molecular sieve and an L-type molecular sieve according to the skeleton topological structure type; the alkali metal ion is at least one selected from K ion, rb ion and Cs ion.
7. The reaction for preparing styrene by toluene side chain alkylation is characterized in that toluene and methanol react to generate styrene in the presence of a catalyst;
the catalyst is selected from the catalyst prepared by the preparation method of any one of claims 1 to 6;
preferably, the reaction adopts a fluidized bed reactor;
preferably, the molar ratio of the toluene to the methanol is 0.1-10, and the total space velocity of the toluene and the methanol is 0.5-8 h -1 The reaction temperature is 300 toThe reaction pressure is 0-20 MPa (gauge pressure) at 500 ℃.
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QIAO HAN ET AL.: ""Efficient synthesis of styrene from toluene with MeOH: Via a ternary composite catalyst"", 《APPLIED CATALYSIS A, GENERAL》, vol. 605, pages 117807 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
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