CN115318287A - Catalyst for preparing styrene by toluene side chain alkylation and preparation method and application thereof - Google Patents
Catalyst for preparing styrene by toluene side chain alkylation and preparation method and application thereof Download PDFInfo
- Publication number
- CN115318287A CN115318287A CN202111544886.2A CN202111544886A CN115318287A CN 115318287 A CN115318287 A CN 115318287A CN 202111544886 A CN202111544886 A CN 202111544886A CN 115318287 A CN115318287 A CN 115318287A
- Authority
- CN
- China
- Prior art keywords
- solution
- sepiolite
- drying
- ion exchange
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000003944 tolyl group Chemical group 0.000 title claims abstract description 18
- 230000029936 alkylation Effects 0.000 title claims abstract description 17
- 239000004113 Sepiolite Substances 0.000 claims abstract description 50
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 50
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000005470 impregnation Methods 0.000 claims abstract description 31
- 238000005342 ion exchange Methods 0.000 claims abstract description 29
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000010306 acid treatment Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- -1 cesium ions Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 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
- 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 2
- 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 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 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
- 238000011160 research Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/66—Silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/66—Silver or gold
- C07C2523/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/18—Phosphorus; Compounds thereof containing oxygen with metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst for preparing styrene by toluene side chain alkylation and a preparation method and application thereof, belonging to the technical field of catalyst preparation and chemical industry. The preparation method takes sepiolite as a matrix and is prepared by acid treatment, alkali treatment, ion exchange and impregnation load modification. The catalyst has the characteristics of high catalytic activity and low raw material price, and can efficiently catalyze the side-chain alkylation reaction of toluene to prepare styrene in one step.
Description
Technical Field
The invention relates to a catalyst for preparing styrene by toluene side chain alkylation and a preparation method and application thereof, belonging to the technical field of catalyst preparation and chemical industry.
Background
Styrene (SM), the most basic aromatic chemical, is the largest chemical used in benzene derivatives. The process for preparing styrene by toluene methanol side chain alkylation is considered to be a styrene production route with potential industrial application value. Compared with the traditional ethylbenzene dehydrogenation production technology, the process takes toluene and methanol as raw materials, not only has the advantage of raw material price, but also can produce styrene in one step under a mild condition, omits the step of preparing styrene by ethylbenzene dehydrogenation, greatly reduces the energy consumption and equipment investment, and has huge industrial application prospect.
The lack of highly active catalysts is critical to limit the industrial applicability of the toluene side chain alkylation process to styrene. Currently, the research on toluene side chain alkylation catalysts mainly focuses on molecular sieves, wherein the activity of the X-type molecular sieve exchanged with alkali metal is the highest, but the activity of the X-type molecular sieve still cannot meet the requirements of industrialization. In addition, the toluene side chain alkylation catalyst prepared by the X-type molecular sieve has the problems of poor hydrothermal stability, easy inactivation and the like, which further limits the application of the catalyst in the process of preparing styrene by toluene methanol side chain alkylation. The search for more active catalytic materials, particularly non-molecular sieve based catalysts with room for improvement, has been a focus of interest to the scientific and industrial community.
Disclosure of Invention
The invention aims to provide a catalyst for preparing styrene by toluene side chain alkylation and a preparation method and application thereof. The catalyst is prepared by taking sepiolite as a matrix through acid treatment, alkali treatment, ion exchange and impregnation loading modification. The catalyst has the characteristics of high catalytic activity and low raw material price.
Sepiolite is a natural clay mineral with a layered chain structure, and has the characteristics of wide source and low price compared with a molecular sieve synthesized by a hydrothermal process. The sepiolite is modified to have both acid sites and basic sites, and the matched acid and base sites are the key for catalyzing the toluene side-chain alkylation reaction.
In order to remove impurities from natural sepiolite and to increase the specific surface area of the sepiolite material, the natural sepiolite is first subjected to an acid treatment. And (3) carrying out high-pressure alkali treatment on the sepiolite after acid treatment to eliminate excessive B acid sites on the surface of the sepiolite and replace part of magnesium ions in the sepiolite by low-valence ions in an alkali solution, so that the sepiolite has good ion exchange performance. In order to enhance the alkalinity of the sepiolite material and improve the activation capability of the sepiolite material on the toluene side chain, the sepiolite after alkali treatment needs to be further subjected to ion exchange. In order to obtain strong capability of dehydrogenating methanol to generate intermediate species and stabilizing the intermediate species, the sepiolite material is subjected to impregnation load modification treatment.
According to one aspect of the application, a preparation method of the catalyst is provided, sepiolite is used as a precursor, and the catalyst is prepared through acid treatment, alkali treatment, ion exchange and impregnation load modification.
Optionally, the sepiolite is a powder.
Optionally, the exchange ions in the ion exchange are selected from rubidium ions or cesium ions.
Optionally, the loading element in the impregnation loading is at least one selected from copper element, silver element, chromium element, zinc element, cerium element, phosphorus element and boron element, and the loading content is 0.1wt% to 5wt%, based on the total mass of the loading element in the mass of the carrier.
Alternatively, the loading content is 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or any value between any two of the foregoing.
Optionally, the acid treatment is: adding sepiolite into the acid solution, stirring, washing, separating and drying;
the liquid-solid ratio of the acid solution to the sepiolite is (3-100) to 1 (ml: g).
Optionally, the acidic solution is selected from at least one of a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution, and a hydrochloric acid solution; the concentration of the acid solution is 0.1-3 mol/L.
Optionally, the stirring is performed for 0.1 to 10 hours at the temperature of 40 to 90 ℃; the drying temperature is 80-150 ℃.
Alternatively, the liquid-solid ratio of the acidic solution to the sepiolite is 5.
The stirring temperature in the acidic solution is 45 ℃, 50 ℃,55 ℃, 60 ℃, 70 ℃, 75 ℃,80 ℃, or any value between any two of the above; the stirring time is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or any value between any two points.
Optionally, the alkali treatment is: adding the sepiolite after acid treatment into an alkaline solution, stirring, washing, separating and drying;
the liquid-solid ratio of the alkaline solution to the sepiolite after acid treatment is (3-100) to 1 (ml: g).
Optionally, the alkaline solution is an alkali metal hydroxide solution.
Optionally, the alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide; the concentration of the alkaline solution is 0.1-5 mol/L.
Optionally, the stirring is performed for 0.1 to 10 hours at a temperature of between 100 and 250 ℃; the drying temperature is 80-150 ℃.
Optionally, the treatment temperature in the alkaline solution is 120 ℃, 150 ℃, 170 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, or any value between any two of the foregoing; the treatment time is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or any value between any two points.
Optionally, the ion exchange is: adding the sepiolite subjected to alkali treatment into an ion exchange solution, and carrying out exchange, washing, separation and drying;
the liquid-solid ratio of the ion exchange solution to the sepiolite after alkali treatment is (3-100) to 1 (ml: g).
Optionally, the ion exchange solution is at least one of nitrate, carbonate, acetate, chloride and hydroxide of rubidium or cesium, and the concentration is 0.1-5 mol/L;
the drying temperature is 80-150 ℃.
Optionally, the impregnation load is: adding the sepiolite after ion exchange into the impregnation liquid, impregnating, standing, drying and roasting;
optionally, the standing time is 0.1-100 h; the roasting is carried out for 3 to 10 hours at the temperature of between 300 and 700 ℃ in the air atmosphere; the drying temperature is 80-150 ℃.
Optionally, the firing temperature is 350 ℃, 400 ℃, 450 ℃, 500 ℃,550 ℃, 600 ℃, 650 ℃, or any value between any two of the foregoing; the roasting time is 4h, 5h, 6h, 7h, 8h, 9h or any value between any two points.
Optionally, the preparation method comprises the steps of:
(1) Acid treatment: adding sepiolite powder into the acid solution, stirring, washing, separating and drying;
(2) Alkali treatment: adding the sepiolite powder subjected to acid treatment into an alkaline solution, stirring, washing, separating and drying;
(3) Ion exchange: adding the sepiolite powder subjected to alkali treatment into an ion exchange solution, and exchanging, washing, separating and drying;
(4) Impregnation and loading: adding the sepiolite powder subjected to ion exchange into the impregnation liquid, impregnating, standing, drying and roasting to obtain the catalyst.
According to one aspect of the application, a reaction for preparing styrene by toluene side chain alkylation is provided, wherein a raw material containing toluene and methanol reacts with a catalyst in a reactor to prepare styrene;
the catalyst is selected from the catalysts prepared by the preparation method.
OptionallyThe feeding molar ratio of the toluene to the methanol is (0.5-10) to 1; the mass space velocity of the toluene and the methanol is 0.2 to 8h -1 (ii) a The reaction pressure is 0-20 MPa (gauge pressure); the reaction temperature is 300-550 ℃;
the reactor is selected from one of a fixed bed reactor, a moving bed reactor or a fluidized bed reactor.
Alternatively, the feed molar ratio of toluene to methanol is 1, 2; the mass space velocity of the toluene and the methanol is 0.5h -1 、 1h -1 、2h -1 、3h -1 、4h -1 、5h -1 、6h -1 、7h -1 Or any value between any two of the above; the reaction pressure is 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa or any value between any two points; the reaction temperature is 350 ℃, 380 ℃, 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, or any value between any two of the above.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes natural sepiolite as a raw material, prepares a brand new catalyst for preparing styrene by toluene side chain alkylation through acid treatment, alkali treatment, ion exchange and impregnation load modification, has the characteristics of high catalytic activity and low raw material price, and can efficiently catalyze the toluene side chain alkylation reaction to prepare styrene in one step.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
EXAMPLE 1 catalyst preparation
Example 1-1 preparation of catalyst C-1
Weighing 50 parts by weight of sepiolite powder, adding the sepiolite powder into 500 parts by weight of 1mol/L sulfuric acid solution, stirring for 4 hours at the temperature of 80 ℃, washing with deionized water, performing centrifugal separation, and drying at the temperature of 80 ℃. Further adding the dried material into 300 parts by weight of 2mol/L lithium hydroxide solution, uniformly stirring, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, treating for 5 hours at 200 ℃, washing with deionized water, performing centrifugal separation, and drying at 80 ℃. Adding the materials into 300 parts by weight of 0.5mol/L cesium nitrate solution, carrying out ion exchange for 3h at 80 ℃, washing with deionized water, carrying out centrifugal separation, and drying at 80 ℃. Adding 0.5 part by weight of copper nitrate, 0.5 part by weight of silver nitrate and 1 part by weight of boric acid into deionized water with the mass required by the equal-volume impregnation of the materials to prepare equal-volume impregnation liquid, then performing equal-volume impregnation, standing overnight, drying at 120 ℃, roasting at 550 ℃ for 4 hours to obtain a catalyst for preparing styrene by toluene side chain alkylation, and the catalyst is named as C-1.
EXAMPLE 1-2 preparation of catalyst C-2
Weighing 50 parts by weight of sepiolite powder, adding the sepiolite powder into 500 parts by weight of 1.5mol/L nitric acid solution, stirring and processing for 4 hours at the temperature of 80 ℃, washing with deionized water, centrifuging and separating, and drying at the temperature of 80 ℃. Further adding the dried material into 300 parts by weight of 2mol/L sodium hydroxide solution, uniformly stirring, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, treating for 5 hours at 200 ℃, washing with deionized water, performing centrifugal separation, and drying at 80 ℃. Adding the materials into 300 parts by weight of 0.5mol/L cesium chloride solution, carrying out ion exchange for 3 hours at the temperature of 80 ℃, washing with deionized water, carrying out centrifugal separation, and drying at the temperature of 80 ℃. Adding 1 weight part of copper nitrate, 1 weight part of sodium phosphate and 0.5 weight part of boron oxide into deionized water with the required mass for isovolumetric impregnation of the materials to prepare an isovolumetric impregnation liquid, then isovolumetric impregnation, standing overnight, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing styrene by toluene side chain alkylation, which is named as C-2.
Examples 1-3 preparation of catalyst C-3
Weighing 50 parts by weight of sepiolite powder, adding into 500 parts by weight of 1.5mol/L hydrochloric acid solution, stirring at 80 ℃ for 4 hours, washing with deionized water, centrifuging, and drying at 80 ℃. Further adding the dried material into 300 parts by weight of 2mol/L potassium hydroxide solution, uniformly stirring, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, treating for 5 hours at 220 ℃, washing with deionized water, performing centrifugal separation, and drying at 80 ℃. Adding the materials into 300 parts by weight of 0.3mol/L cesium carbonate solution, carrying out ion exchange for 3 hours at the temperature of 80 ℃, washing with deionized water, carrying out centrifugal separation, and drying at the temperature of 80 ℃. Adding 1 part by weight of silver nitrate, 0.5 part by weight of zinc nitrate and 1 part by weight of boric acid into deionized water with the required mass for equal-volume impregnation of the materials to prepare equal-volume impregnation liquid, then performing equal-volume impregnation, standing overnight, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing styrene by alkylating the side chain of toluene, wherein the catalyst is named as C-3.
Examples 1-4 preparation of catalyst C-4
Weighing 50 parts by weight of sepiolite powder, adding the sepiolite powder into 500 parts by weight of 1.5mol/L phosphoric acid solution, stirring and processing for 4 hours at the temperature of 80 ℃, washing with deionized water, centrifuging and separating, and drying at the temperature of 80 ℃. Further adding the dried material into 300 parts by weight of 2mol/L sodium hydroxide solution, uniformly stirring, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, treating for 5 hours at 200 ℃, washing with deionized water, performing centrifugal separation, and drying at 80 ℃. Adding the materials into 300 parts by weight of 0.3mol/L cesium acetate solution, carrying out ion exchange for 3 hours at the temperature of 80 ℃, washing with deionized water, carrying out centrifugal separation, and drying at the temperature of 80 ℃. Adding 1 part by weight of silver nitrate, 0.5 part by weight of cerium nitrate and 1 part by weight of sodium borate into deionized water with the required mass for isovolumetric impregnation of the materials to prepare an isovolumetric impregnation liquid, then isovolumetric impregnation, standing overnight, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing styrene by toluene side chain alkylation, which is named as C-4.
Examples 1-5 preparation of catalyst C-5
Weighing 50 parts by weight of sepiolite powder, adding the sepiolite powder into 500 parts by weight of 1mol/L sulfuric acid solution, stirring for 4 hours at the temperature of 80 ℃, washing with deionized water, performing centrifugal separation, and drying at the temperature of 80 ℃. Further adding the dried material into 300 parts by weight of 2mol/L sodium hydroxide solution, uniformly stirring, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, treating for 5 hours at 200 ℃, washing with deionized water, performing centrifugal separation, and drying at 80 ℃. Adding the materials into 300 parts by weight of 0.3mol/L cesium hydroxide solution, carrying out ion exchange for 3 hours at the temperature of 80 ℃, washing with deionized water, carrying out centrifugal separation, and drying at the temperature of 80 ℃. Adding 1 weight part of silver nitrate, 0.2 weight part of chromium nitrate and 1.2 weight parts of boric acid into deionized water with the required mass for equal-volume impregnation of the materials to prepare equal-volume impregnation liquid, then performing equal-volume impregnation, standing overnight, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing styrene by toluene side chain alkylation, which is named as C-5.
Comparative example
Using 50 parts by weight of a commercially available 13X raw powder (Si/Al = 1.23) as a precursor, exchange was performed 4 times at 80 ℃ with 500 parts by weight of a 0.3mol/L CsCl solution, washing with deionized water, centrifugal separation, and drying at 120 ℃ for 4 hours. Adding 0.5 part by weight of copper nitrate, 0.5 part by weight of silver nitrate and 1 part by weight of boric acid into deionized water with the mass required by the equal-volume impregnation of the materials to prepare equal-volume impregnation liquid, then performing equal-volume impregnation, standing overnight, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the comparative catalyst.
Example 2 evaluation of toluene methanol side chain alkylation Performance
The catalysts C-1, C-2, C-3, C-4, C-5 prepared in example 1 and prepared in comparative example were subjected to evaluation of the performance of the side-chain alkylation reaction with toluene and methanol using a fixed bed reactor having an inner diameter of 8mm and a catalyst loading of 2g. The raw materials of toluene and methanol are pumped in by a plunger pump, the feeding molar ratio of the toluene and the methanol is shown in Table 1, and the feeding airspeed of the toluene and the methanol is 2h -1 The reaction temperature was 430 ℃ and the reaction pressure was atmospheric.
The product was analysed by Agilent 7890A chromatography. Separating hydrocarbon components by Agilent CP-WAX 25m × 32 μm × 1.2 μm capillary column, detecting with FID detector, and detecting CO and CO 2 And H 2 Separated by a Porapark Q4 m multiplied by 1/8' packed column and detected by 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 evaluation results are shown in table 1.
TABLE 1 performances of the toluene methanol side-alkylation reaction
* The reaction was sampled and analyzed 1 time every 1 hour, and the results of the above reaction were averaged over 8 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 (8)
1. A process for preparing the catalyst used to prepare styrene by alkylating the side chain of toluene features that the sepiolite is used as mother body and includes acid treatment, alkali treatment, ion exchange and immersion modification.
2. The production method according to claim 1, wherein the exchange ions in the ion exchange are selected from rubidium ions or cesium ions;
preferably, the load element in the impregnation load modification is at least one element selected from copper element, silver element, chromium element, zinc element, cerium element, phosphorus element and boron element, and the load amount is 0.1wt% to 5wt%.
3. The method of claim 1, wherein the acid treatment is: adding sepiolite into the acid solution, stirring, washing, separating and drying;
the liquid-solid ratio of the acidic solution to the sepiolite is (3-100) to 1 (ml: g);
preferably, the acid solution is at least one selected from sulfuric acid solution, nitric acid solution, phosphoric acid solution and hydrochloric acid solution; the concentration of the acid solution is 0.1-3 mol/L;
preferably, the acid treatment is characterized in that the stirring treatment is carried out for 0.1 to 10 hours at the temperature of between 40 and 90 ℃; the drying temperature is 80-150 ℃.
4. The method of claim 1, wherein the alkali treatment is: adding the sepiolite after acid treatment into an alkaline solution, stirring, washing, separating and drying;
the liquid-solid ratio of the alkaline solution to the sepiolite after acid treatment is (3-100) to 1 (ml: g);
preferably, the alkaline solution is an alkali metal hydroxide solution;
preferably, the alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide; the concentration of the alkaline solution is 0.1-5 mol/L;
preferably, the alkali treatment is characterized in that the stirring treatment is carried out for 0.1 to 10 hours at the temperature of between 100 and 250 ℃; the drying temperature is 80-150 ℃.
5. The production method according to claim 1, wherein the ion exchange is: adding the sepiolite subjected to alkali treatment into an ion exchange solution, and carrying out exchange, washing, separation and drying;
the liquid-solid ratio of the ion exchange solution to the sepiolite after the alkali treatment is (3-100) to 1 (ml: g);
preferably, the ion exchange solution is at least one of nitrate, carbonate, acetate, chloride and hydroxide of rubidium or cesium, and the concentration is 0.1-5 mol/L; the drying temperature is 80-150 ℃.
6. The method of claim 1, comprising the steps of:
(1) Acid treatment: adding sepiolite powder into the acid solution, stirring, washing, separating and drying;
(2) Alkali treatment: adding the sepiolite powder subjected to acid treatment into an alkaline solution, stirring, washing, separating and drying;
(3) Ion exchange: adding the sepiolite powder subjected to alkali treatment into an ion exchange solution, and carrying out exchange, washing, separation and drying;
(4) Impregnation and loading: adding the sepiolite powder after ion exchange into the impregnation liquid, impregnating, standing, drying and roasting to obtain the catalyst.
7. A reaction for preparing styrene by toluene side chain alkylation is characterized in that a raw material containing toluene and methanol reacts with a catalyst in a reactor to prepare styrene;
the catalyst is selected from the catalysts prepared by the preparation method of any one of claims 1 to 6.
8. The reaction of claim 7, wherein the feed molar ratio of toluene to methanol is (0.5-10): 1; the mass space velocity of the toluene and the methanol is 0.2 to 8h -1 (ii) a The reaction pressure is 0-20 MPa (gauge pressure); the reaction temperature is 300-550 ℃;
the reactor is selected from one of a fixed bed reactor, a moving bed reactor or a fluidized bed reactor.
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