CN116062769A - Hydrogen ZSM-5 molecular sieve and preparation method thereof, and xylene isomerization catalyst and preparation method thereof - Google Patents
Hydrogen ZSM-5 molecular sieve and preparation method thereof, and xylene isomerization catalyst and preparation method thereof Download PDFInfo
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- CN116062769A CN116062769A CN202111272654.6A CN202111272654A CN116062769A CN 116062769 A CN116062769 A CN 116062769A CN 202111272654 A CN202111272654 A CN 202111272654A CN 116062769 A CN116062769 A CN 116062769A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 141
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 47
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000008096 xylene Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 26
- 239000001257 hydrogen Substances 0.000 title claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229940006460 bromide ion Drugs 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 25
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 terephthalic acid diester Chemical class 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000006204 deethylation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble 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
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Abstract
The invention relates to a hydrogen-type ZSM-5 molecular sieve and a preparation method thereof, and a dimethylbenzene isomerization catalyst and a preparation method thereof, wherein the method comprises the following steps: mixing a silicon source, an aluminum source, a template agent and water to obtain a molecular sieve synthesized mixed material; crystallizing the molecular sieve synthesized mixture material at 140-190 ℃ under autogenous pressure for 40-140 hours, collecting solids and drying; siO in the molecular sieve synthesized mixture 2 /Al 2 O 3 The molar ratio of (2) is 20-180, template agent, water and SiO 2 The molar ratio of (2) is 0.2-1: 10 to 60:1, wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting; the template agent is selected from quaternary ammonium baseAnd/or quaternary ammonium salts. The hydrogen-type ZSM-5 molecular sieve prepared by the method does not need to carry out an ion exchange process, so that the emission of ammonia nitrogen wastewater in the preparation process can be reduced, and the method is more environment-friendly; meanwhile, the method can simplify the preparation flow of the catalyst, shorten the preparation period, improve the preparation efficiency and increase the isomerization activity and the xylene yield of the catalyst.
Description
Technical Field
The invention relates to a preparation method and application of a ZSM-5 molecular sieve, in particular to a hydrogen ZSM-5 molecular sieve and a preparation method thereof, and a dimethylbenzene isomerization catalyst taking the hydrogen ZSM-5 molecular sieve prepared by the method as an active component and a preparation method thereof.
Background
Para-xylene (PX) is an important chemical raw material, and is mainly used for producing terephthalic acid, terephthalic acid diester, and phthalic anhydride, and in addition, it is also used in the fields of paint, dye, pesticide, medicine, and the like. With the continuous development of the industries in China, the demand of PX is rapidly increased. In order to meet the market demand, the construction scale of an aromatic hydrocarbon combined device mainly used for producing PX, which consists of technical units such as C8 aromatic hydrocarbon isomerization, xylene rectification, adsorption or crystallization separation and the like, is continuously enlarged. Among them, the xylene isomerization technology for increasing the yield of PX is a key means for converting ethylbenzene, meta-xylene and ortho-xylene into PX. In general, the aromatic hydrocarbon combination unit separates pure paraxylene by using traditional crystallization or molecular sieve adsorption methods, and then separates a small amount of light non-aromatic hydrocarbon, benzene, toluene and C9+ heavy aromatic hydrocarbon, and the residual C8 aromatic hydrocarbon material can be used as an isomerization raw material. Through the reaction of the xylene isomerization unit, three isomers of the xylene reach or approach thermodynamic equilibrium composition, namely, the xylene contains 52 to 54 mass percent of meta-xylene, 23 to 24 mass percent of para-xylene and 23 to 24 mass percent of ortho-xylene, and the xylene is recycled to the separation unit for purifying the para-xylene. In addition, in the prior art, no matter the mode of high-efficiency rectification or adsorption separation is adopted, the separation of ethylbenzene and dimethylbenzene in C8 aromatic hydrocarbon is huge. Thus, the ethylbenzene needs to be converted simultaneously during xylene isomerization. There are two different ways of ethylbenzene conversion: one is the conversion of ethylbenzene to xylenes and the other is the deethylation of ethylbenzene to benzene. At present, the technology adopting the ethylbenzene deethylation type isomerization catalyst has the advantages of lower operation energy consumption control, relatively smaller device scale control, better technical economy and the like, and is widely adopted.
CN1044053a discloses a C8 aromatic hydrocarbon isomerization catalyst and a preparation method thereof, wherein the catalyst carrier comprises 10-80 mass% of mordenite and 20-90 mass% of alumina, and 0.01-2.0 mass% of group viii metal is loaded. The catalyst is typically an ethylbenzene conversion isomerization catalyst.
The alkyl arene isomerization catalyst disclosed in CN1887423A is an ethylbenzene deethylation isomerization catalyst, the active component is mainly high-silicon five-membered ring zeolite, preferably ZSM-5 molecular sieve or eutectic structure zeolite of the high-silicon five-membered ring zeolite and ZSM-11, and the catalyst further comprises 1.0 to 4.5 mass percent of mordenite. The catalyst has better deethylation performance and better arene isomerization performance.
The raw powder of molecular sieve for isomerization catalyst is usually sodium type, and needs to be ion-exchanged with ammonium salt to be converted into ammonium type, and then NH is obtained by roasting 3 The hydrogen form is obtained after the removal.
CN101896270a discloses a xylene isomerization catalyst requiring ion exchange, the active component of the catalyst preferably being a ZSM-5 molecular sieve, the binder comprising amorphous phosphorus-containing alumina having a platinum content of no more than 350 ppm by weight. The ion exchange step is carried out after shaping of the support, the solution used for ion exchange generally comprising at least one source of hydrogen-forming cations, such as NH 4 + . The hydrogen ions formed are used as cations to exchange ions with alkali metal cations, thereby exchanging the alkali metal cations for NH 4 + And then roasting to obtain the hydrogen molecular sieve. Examples of the salt solution of ion exchange which meets the conditions include ammonium nitrate, ammonium sulfate, ammonium chloride and the like.
In order to optimize the preparation flow of the molecular sieve and reduce the emission of ammonia nitrogen wastewater, the green preparation technology of the catalyst is researched, and the hydrogen type molecular sieve is prepared by adopting a one-step method, so that the subsequent ion exchange process is omitted. In the document Direct synthesis of b-axis oriented H-form ZSM-5zeolites with an enhanced performance in the methanol to propylene reaction, a one-step synthesis method is adopted to directly synthesize a hydrogen-type ZSM-5 molecular sieve, and the molecular sieve is applied to the reaction of preparing propylene from methanol. The influence of the morphology, crystallinity, aperture, specific surface area, acidity of the molecular sieve and the like on the catalytic activity of the catalyst is examined, and glucose is used as a surfactant in the synthesis process, and the glucose is added into a synthesis system to cause difficulty in subsequent washing work.
Disclosure of Invention
The invention aims to provide a method for preparing a hydrogen ZSM-5 molecular sieve, a de-ethylated xylene isomerization catalyst containing the hydrogen ZSM-5 molecular sieve and a preparation method thereof, wherein the xylene isomerization catalyst can be prepared without ion exchange of the molecular sieve and has higher isomerization activity and xylene yield.
To achieve the above object, a first aspect of the present invention provides a method for preparing a hydrogen form ZSM-5 molecular sieve, the method comprising: mixing a silicon source, an aluminum source, a template agent and water to obtain a molecular sieve synthesized mixed material; crystallizing the molecular sieve synthesized mixture at 140-190 ℃ under autogenous pressure for 40-140 hours, collecting solids and drying; in the molecular sieve synthesis mixture, siO 2 /Al 2 O 3 The molar ratio of (2) is 20-180, the template agent: water: siO (SiO) 2 The molar ratio of (2) is 0.2-1: 10 to 60:1, wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting; the template agent is selected from quaternary ammonium base and/or quaternary ammonium salt.
Optionally, the method for preparing the hydrogen form ZSM-5 molecular sieve according to the first aspect further comprises: the molecular sieve synthesis mixture further comprises a pH regulator, wherein the pH regulator is combined with SiO 2 The molar ratio of the pH regulator is 0.22 to 1.5, and the pH regulator is NH 3 ·H 2 O and/or NH 4 Cl。
Alternatively, the template has the general formula N (R) 4 X, wherein R is selected from alkyl with 1-4 carbon atoms, and X is hydroxide ion, chloride ion or bromide ion; in the molecular sieve synthesis mixture, the template agent and SiO 2 The molar ratio of (2) is 0.3-1.
Optionally, in the molecular sieve synthesis mixture, the SiO 2 /Al 2 O 3 The molar ratio of water/SiO is 25-110 2 The molar ratio of (2) is 10-40.
Optionally, the silicon source is silica sol and/or silica gel; siO in the silica sol 2 The content of (2) is 10-40% by mass; the particle size of the silica gel is 0.005-0.05 mu m; the aluminum source is aluminum nitrate and/or aluminum sulfate.
Optionally, the crystallization treatment temperature is 160-185 ℃; the crystallization treatment time is 90-130 h.
Optionally, the hydrogen form ZSM-5 molecular sieve has an average grain size of 0.05 to 10 μm.
In a second aspect of the invention, the hydrogen-type ZSM-5 molecular sieve prepared by the method in the first aspect of the invention is used.
In a third aspect, the present invention provides a xylene isomerization catalyst comprising a support and platinum supported on the support; the carrier comprises 20 to 90 mass percent of alumina and 10 to 80 mass percent of hydrogen-type ZSM-5 molecular sieve according to the second aspect of the invention, and the content of platinum is 0.01 to 0.6 mass percent based on the carrier.
In a fourth aspect, the present invention provides a process for preparing the xylene isomerization catalyst according to the third aspect of the present invention, the process comprising: mixing the hydrogen ZSM-5 molecular sieve according to the second aspect of the invention with pseudo-boehmite, adding an acid solution, kneading, forming, drying and roasting to obtain a carrier, impregnating the carrier with a platinum-containing compound solution, and drying the impregnated solid at 100-140 ℃ for 8-24 hours; then roasting for 2-24 h in air atmosphere at 520-550 ℃; and then reducing with hydrogen at 400-550 ℃.
Optionally, the platinum-containing compound is chloroplatinic acid.
According to the technical scheme, the hydrogen ZSM-5 molecular sieve is synthesized by adopting the method disclosed by the invention through a one-step method, an ion exchange process is not needed, the emission of ammonia nitrogen wastewater in the preparation process can be reduced, and the method is more environment-friendly; meanwhile, the method can simplify the preparation flow of the catalyst, shorten the preparation period and improve the preparation efficiency; the catalyst prepared by the method can show higher isomerization activity and xylene yield.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is an X-ray diffraction (XRD) spectrum of ZSM-5 molecular sieves prepared in examples and comparative examples of the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of ZSM-5 molecular sieves prepared in examples and comparative examples according to the invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect, the present invention provides a process for preparing a hydrogen form of a ZSM-5 molecular sieve, the process comprising: mixing a silicon source, an aluminum source, a template agent and water to obtain a molecular sieve synthesized mixed material; crystallizing the molecular sieve synthesized mixture at 140-190 ℃ under autogenous pressure for 40-140 hours, collecting solids and drying; in the molecular sieve synthesis mixture, siO 2 /and Al 2 O 3 The molar ratio of (2) is 20-180, the template agent: water: siO (SiO) 2 The molar ratio of (2) is 0.2-1: 10 to 60:1, wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting; the template agent is selected from quaternary ammonium base and/or quaternary ammonium salt.
According to the technical scheme, the hydrogen ZSM-5 molecular sieve is synthesized by adopting the method disclosed by the invention through a one-step method, an ion exchange process is not needed, the emission of ammonia nitrogen wastewater in the preparation process can be reduced, and the method is more environment-friendly; meanwhile, the method can simplify the preparation flow of the catalyst, shorten the preparation period and improve the preparation efficiency. The catalyst prepared by the method can show higher isomerization activity and xylene yield. The hydrogen ZSM-5 molecular sieve is preferably synthesized by adopting a homogeneous reactor dynamic synthesis method.
In one embodiment, the method further comprises: in the step of mixing, adding a pH regulator, namely the molecular sieve synthesis mixture further comprises the pH regulator, wherein the pH regulator is mixed with SiO 2 The molar ratio of (2) is preferably 0.22 to 1.5, more preferably 0.22 to 1.0; preferably, the pH is adjustedThe festival agent is ammonia water and/or ammonium salt, and further, the pH regulator is NH 3 ·H 2 O and/or NH 4 Cl。
In the embodiment, the pH regulator is added in the process of preparing the molecular sieve, so that the pH value of the molecular sieve synthesis mixture can be regulated, and the prepared hydrogen ZSM-5 molecular sieve raw powder can show excellent performance; wherein the pH regulator is NH 3 ·H 2 In an embodiment of O, the pH adjustor is used in an amount such that NH 3 ·H 2 O and SiO 2 The molar ratio of (2) is 0.8 or less, for example, 0.3 to 0.8; the pH regulator is NH 4 In embodiments of Cl, the pH adjuster is used in an amount such that NH 4 Cl and SiO 2 The molar ratio of (2) is below 0.4, for example, 0.22-0.4, so that the performance of the hydrogen-type ZSM-5 molecular sieve raw powder can be further enhanced; in other embodiments of the invention, no pH adjuster may be added during the molecular sieve preparation process.
In one embodiment, the template has the general formula N (R) 4 X, wherein R is selected from alkyl with 1-4 carbon atoms, preferably ethyl and/or propyl, X is hydroxide ion, chloride ion or bromide ion, preferably hydroxide ion; in the molecular sieve synthesis mixture, the template agent and SiO 2 The molar ratio of (2) may be 0.3 to 1, preferably 0.4 to 0.8. In a further preferred embodiment of the invention, the templating agent is selected from N (C 3 H 7 ) 4 OH and/or N (C) 3 H 7 ) 4 Br。
In one embodiment, in the mixed material, siO 2 With Al 2 O 3 The molar ratio of (2) is 25 to 110, preferably 30 to 100, water/SiO 2 The molar ratio of (2) is preferably 10 to 40. In this embodiment, in the mixture, siO 2 With Al 2 O 3 Molar ratio of water/SiO 2 Is preferably carried out in a molar ratio which reduces the water consumption and produces SiO 2 With Al 2 O 3 Hydrogen form ZSM-5 molecular sieve with wide molar ratio range.
In one embodiment, the silicon source is a silica sol and/or a silica gel, preferably the silicon source is free of alkali metal cations, i.e. the silicon source is free ofSilica sols containing alkali metal cations and/or silica gels containing no alkali metal cations; the alkali metal cation is sodium and/or potassium; further, siO in the silica sol 2 The content is 10 to 40 mass%, preferably 20 to 40 mass%; the particle size of the silica gel is 0.005-0.05 mu m, preferably 0.01-0.03 mu m; the aluminium source may be a soluble salt of aluminium, for example aluminium nitrate and/or aluminium sulphate, preferably aluminium nitrate.
In one embodiment, the crystallization treatment is carried out at a temperature of 160 to 185 ℃, preferably 175 to 185 ℃; the time of the crystallization treatment is preferably 90-130 h; the method further comprises the steps of: after the crystallization treatment, the solid is collected and dried. The drying temperature is preferably 100-140 ℃ and the time is preferably 8-24 hours. In this embodiment, the hydrogen form ZSM-5 molecular sieve activity can be further enhanced by optimizing the crystallization reaction conditions.
In one embodiment, the hydrogen form ZSM-5 molecular sieve has an average crystallite size of 0.05 to 10. Mu.m, preferably 0.1 to 1. Mu.m.
In a second aspect of the invention, the hydrogen-type ZSM-5 molecular sieve prepared by the method in the first aspect of the invention is used.
In a third aspect, the present invention provides a xylene isomerization catalyst comprising a support and platinum supported on the support; the carrier comprises alumina and the hydrogen-form ZSM-5 molecular sieve according to the second aspect of the invention, wherein the content of the hydrogen-form ZSM-5 molecular sieve is 10-80% by mass, preferably 40-75% by mass, the content of the alumina is 20-90% by mass, preferably 25-60% by mass, and the content of the platinum is 0.01-0.6% by mass, preferably 0.02-0.5% by mass, based on the total mass of the carrier.
In a fourth aspect, the present invention provides a process for preparing the xylene isomerization catalyst according to the third aspect of the present invention.
In one embodiment, the method comprises: mixing the hydrogen ZSM-5 molecular sieve according to the second aspect of the invention with pseudo-boehmite, adding an acid solution, kneading, forming, drying and roasting to obtain a carrier, wherein the acid solution is preferably nitric acid solution. The carrier is put intoImpregnating with a platinum compound-containing solution, preferably at a temperature of 20-40 ℃, for a time of preferably 10-50 hours. Drying the solid obtained after impregnation at 100-140 ℃ for 8-24 h; then roasting for 2-24 h in air atmosphere at 520-550 ℃; and then reducing with hydrogen at 400-550 deg.c for 2-10 hr. Wherein, the roasting can be carried out in static atmosphere without air flow or at a volume space velocity of 50-500 h -1 Is performed in a dynamic atmosphere. Preferably, the platinum-containing compound is chloroplatinic acid. The drying temperature for preparing the carrier is preferably 100-140 ℃ and the time is preferably 8-24 hours; the roasting temperature is preferably 520-650 ℃ and the time is preferably 2-8 hours.
The xylene isomerization catalyst provided by the invention can be used for xylene isomerization reaction of C8 aromatic hydrocarbon, wherein the method for isomerization reaction can comprise the following steps: contacting a C8 aromatic hydrocarbon-containing raw material with the dimethylbenzene isomerization catalyst in the presence of hydrogen to carry out isomerization reaction. The reaction conditions of the isomerization reaction include: the reaction temperature is 340-440 ℃, preferably 360-420 ℃; the reaction pressure is 0.4-2.5 MPa, preferably 0.6-2.0 MPa; the molar ratio of the hydrogen to the C8 aromatic hydrocarbon is 0.5-4.0: 1. preferably 1.0 to 2.0:1, a step of; the space velocity of the feeding mass is 4.0 to 25.0h -1 Preferably 6.0 to 18.0h -1 。
The invention is illustrated in further detail by the following examples. The starting materials used in the examples are all available commercially.
Example 1
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 30g of neutral silica sol having a content of 30 mass%, 1.88g of aluminum nitrate nonahydrate, and tetrapropylammonium hydroxide [ N (C) 3 H 7 ) 4 OH]61g of solution, 3.4g of ammonia water solution with the concentration of 25 mass percent and 1.844g of deionized water are evenly mixed to obtain a molecular sieve synthesized mixed material, wherein N (C) 3 H 7 ) 4 OH is used as a template agent, NH 3 ·H 2 O is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (3) is 60, the template agent: h 2 O：SiO 2 : the molar ratio of the pH regulator is 0.5:26.67:1:0.333. and crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 180 ℃ under autogenous pressure and stirring for 96 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-1.
(2) Preparation of the catalyst
Mixing Z-1 with pseudo-boehmite according to Z-1: alumina was 7:3, fully mixing and grinding uniformly. Adding nitric acid aqueous solution with the content of 3 mass percent accounting for 6 mass percent of the solid into the mixture to prepare a viscous mixture, and extruding the mixture into strips. The pellets were dried at 120℃for 10 hours, then pelletized, and calcined in an atmosphere of air at 550℃for 4 hours to obtain a carrier containing 70 mass% of Z-1 molecular sieve and 30 mass% of alumina. 3g of the carrier was immersed in 10 ml of an aqueous solution of chloroplatinic acid containing 0.003 g of platinum at 20℃for 24 hours, the immersed solid was dried at 120℃for 12 hours, calcined at 500℃for 5 hours, and then reduced at 450℃for 4 hours in a hydrogen atmosphere to prepare catalyst C-1, wherein the platinum content was 0.03 mass% based on the carrier.
Example 2
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 30g of neutral silica sol having a content of 30 mass%, 3.75g of aluminum nitrate nonahydrate, and tetrapropylammonium hydroxide [ N (C) 3 H 7 ) 4 OH]73.2g of solution, 6.12g of ammonia water solution with the concentration of 25 mass percent and 0.68g of deionized water are evenly mixed to obtain a molecular sieve synthesized mixed material, wherein N (C) 3 H 7 ) 4 OH is used as a template agent, NH 3 ·H 2 O is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (2) is 30, the template agent: h 2 O：SiO 2 : the molar ratio of the pH regulator is 0.6:30.6:1:0.6. and (3) crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 175 ℃ under autogenous pressure and stirring for 120 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-2.
(2) Preparation of the catalyst
Catalyst C-2 was prepared as in example 1, except that Z-2 was used, and the platinum content was 0.03 mass% based on the carrier.
Example 3
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 22.5g of neutral silica sol with 40 mass percent, 2.81g of aluminum nitrate nonahydrate and tetrapropylammonium hydroxide with 25 mass percent of concentration 3 H 7 ) 4 OH]54.9g of solution, 2.8g of NH 4 Cl and 0.8g deionized water are uniformly mixed to obtain a molecular sieve synthesized mixed material, wherein N (C) 3 H 7 ) 4 OH is used as a template agent, NH 4 Cl is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (2) is 40, the template agent: h 2 O：SiO 2 : the molar ratio of the pH regulator is 0.45:21:1:0.35. and (3) crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 175 ℃ under autogenous pressure and stirring for 110 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-3.
(2) Preparation of the catalyst
Catalyst C-3 was prepared as in example 1, except that Z-3 was used, and the platinum content was 0.03 mass% based on the carrier.
Example 4
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 22.5g of neutral silica sol with 40 mass percent, 1.25g of aluminum nitrate nonahydrate and tetrapropylammonium hydroxide with 25 mass percent of concentration 3 H 7 ) 4 OH]54.23g of solution, 1.783g of NH 4 Cl and 5.29g deionized water are uniformly mixed to obtain a molecular sieve synthesized mixture, wherein N (C) 3 H 7 ) 4 OH is used as a template agent, NH 4 Cl is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (2) is 90, the template agent: h 2 O：SiO 2 : molar ratio of pH regulator0.44:22.2:1:0.22. and crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 185 ℃ under autogenous pressure and stirring for 100 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-4.
(2) Preparation of the catalyst
Catalyst C-4 was prepared as in example 1, except that Z-4 was used, and the platinum content was 0.03 mass% based on the carrier.
Example 5
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 30g of neutral silica sol having a content of 30 mass%, 1.125g of aluminum nitrate nonahydrate, and tetrapropylammonium hydroxide [ N (C) 3 H 7 ) 4 OH]58.56g of the solution is uniformly mixed with 0.71g of deionized water to obtain a molecular sieve synthesized mixture, wherein N (C) 3 H 7 ) 4 OH is used as a template agent. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (2) is 100, the template agent: h 2 O：SiO 2 =0.48: 25:1. and (3) crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 180 ℃ under autogenous pressure and stirring for 100 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-5.
(2) Preparation of the catalyst
Catalyst C-5 was prepared as in example 1, except that Z-5 was used, and the platinum content was 0.03 mass% based on the carrier.
Example 6
(1) Preparation of molecular sieves
SiO was added to a 200mL reactor 2 30g of neutral silica sol having a content of 30 mass%, 1.406g of aluminum nitrate nonahydrate, 19.969g of tetrapropylammonium bromide [ N (C) 3 H 7 ) 4 Br]7.69g of ammonia water solution with the concentration of 25 mass percent and 33.54g of deionized water are uniformly mixed to obtain a molecular sieve synthesized mixed material, wherein [ N (C) 3 H 7 ) 4 Br]As a template agent, NH 3 ·H 2 O is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (3) is 80, the template agent: h 2 O：SiO 2 : the molar ratio of the pH regulator is 0.5:15:1:0.75. and (3) crystallizing the molecular sieve synthesized mixture in a closed reaction kettle at 180 ℃ under autogenous pressure and stirring for 100 hours, collecting crystallized solid, washing the crystallized solid with deionized water until washing water is neutral, and drying the washed solid at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-6.
(2) Preparation of the catalyst
Catalyst C-6 was prepared as in example 1, except that Z-6 was used, and the platinum content was 0.03 mass% based on the carrier.
Comparative example 1
(1) Preparation of molecular sieves
Molecular sieves were prepared as in example 1, step (1), except that 2g of NaOH was used in place of NH 3 ·H 2 O, and preparing the sodium ZSM-5 molecular sieve Z-7.
(2) Preparation of the catalyst
The molecular sieve Z-7 prepared by the method is prepared by mixing Z-7 with pseudo-boehmite according to Z-7: alumina was 7:3, fully mixing and grinding uniformly. Adding 3 mass% nitric acid aqueous solution accounting for 6 mass% of the solid to prepare a viscous mixture, extruding and molding. Drying the bar at 120 ℃ for 10 hours, then granulating, roasting for 4 hours in an atmosphere of 550 ℃ air, carrying out ion exchange for 4 hours by using a 4% ammonium chloride aqueous solution under the water bath condition of 90 ℃, washing the solid obtained after the ion exchange until no chloride ions exist in the washing liquid, and drying at 120 ℃ for 6 hours to obtain the carrier, wherein the carrier contains 70 mass% of Z-7 molecular sieve and 30 mass% of alumina. 3g of the carrier was immersed in 10 ml of an aqueous solution of chloroplatinic acid containing 0.003 g of platinum at 20℃for 24 hours, the immersed solid was dried at 120℃for 12 hours, calcined at 500℃for 5 hours, and then reduced at 450℃for 4 hours in a hydrogen atmosphere to prepare catalyst D-1, wherein the platinum content was 0.03 mass% based on the carrier.
Comparative example 2
Catalyst D-2 was prepared by the catalyst preparation method of step (2) in example 1 using sodium ZSM-5 molecular sieve powder Z-7 prepared in comparative example 1.
Comparative example 3
Molecular sieves were prepared by the procedure of example 3, step (1), except that 3g of NaOH was used instead of NH 4 Cl, and the sodium ZSM-5 molecular sieve Z-8 is prepared.
The molecular sieve Z-8 prepared by the method is prepared by mixing Z-8 with pseudo-boehmite according to Z-8: alumina was 7:3, fully mixing and grinding uniformly. Adding 3 mass% nitric acid aqueous solution accounting for 6 mass% of the solid to prepare a viscous mixture, extruding and molding. Drying the bar at 120 ℃ for 10 hours, then granulating, roasting for 4 hours in the atmosphere of 550 ℃ air, carrying out ion exchange for 3 hours by using 5% ammonium chloride aqueous solution under the water bath condition of 95 ℃, washing the solid obtained after the ion exchange until no chloride ions exist in the washing liquid, and drying at 120 ℃ for 6 hours to obtain the carrier, wherein the carrier contains 70 mass% of Z-8 molecular sieve and 30 mass% of alumina. 3g of the carrier was immersed in 10 ml of an aqueous solution of chloroplatinic acid containing 0.003 g of platinum at 20℃for 24 hours, the immersed solid was dried at 120℃for 12 hours, calcined at 500℃for 5 hours, and then reduced at 450℃for 4 hours in a hydrogen atmosphere to prepare catalyst D-3, wherein the platinum content was 0.03 mass% based on the carrier.
Comparative example 4
Catalyst D-4 was prepared as in catalyst preparation in step (2) of example 1 using sodium ZSM-5 molecular sieve powder Z-8 prepared in comparative example 3.
Comparative example 5
Molecular sieves were prepared as in step (1) of example 5 except that 4g of NaOH was added to the synthesis batch to produce sodium ZSM-5 molecular sieve Z-9.
The molecular sieve Z-9 prepared by the method is prepared by mixing Z-9 with pseudo-boehmite according to Z-9: alumina was 7:3, fully mixing and grinding uniformly. Adding 3 mass% nitric acid aqueous solution accounting for 6 mass% of the solid to prepare a viscous mixture, extruding and molding. Drying the bar at 120 ℃ for 10 hours, then granulating, roasting for 4 hours in the air atmosphere at 550 ℃, carrying out ion exchange for 5 hours by using a 6% ammonium chloride aqueous solution under the water bath condition at 85 ℃, washing the solid obtained after the ion exchange until no chloride ions exist in the washing liquid, and drying at 120 ℃ for 6 hours to obtain the carrier, wherein the carrier contains 70 mass% of Z-9 molecular sieve and 30 mass% of alumina. 3g of the carrier was immersed in 10 ml of an aqueous solution of chloroplatinic acid containing 0.003 g of platinum at 20℃for 24 hours, the immersed solid was dried at 120℃for 12 hours, calcined at 500℃for 5 hours, and then reduced at 450℃for 4 hours in a hydrogen atmosphere to prepare catalyst D-5, wherein the platinum content was 0.03 mass% based on the carrier.
Comparative example 6
Catalyst D-6 was prepared according to the catalyst preparation method of example 1, step (2), using sodium ZSM-5 molecular sieve powder Z-9 prepared in comparative example 5.
Comparative example 7
SiO was added to a 200mL reactor 2 22.5g of neutral silica sol with 40 mass percent, 2.251g of aluminum nitrate nonahydrate and tetrapropylammonium hydroxide with 25 mass percent of concentration (N (C) 3 H 7 ) 4 OH]19.52g of solution, 2.04g of ammonia water solution with the concentration of 25 mass percent and 131.35g of deionized water are uniformly mixed to obtain a molecular sieve synthesized mixed material, wherein N (C) 3 H 7 ) 4 OH is used as a template agent, NH 3 ·H 2 O is a pH regulator. In the mixed material, siO 2 /Al 2 O 3 The molar ratio of (2) is 50, the template agent: h 2 O：SiO 2 : the molar ratio of the pH regulator is 0.16:60:1:0.2. crystallizing the molecular sieve synthesis mixture in a closed reaction kettle at 185 ℃ under autogenous pressure and stirring for 110 hours, collecting crystallized solid, washing with deionized water until washing water is neutral, and drying at 120 ℃ for 12 hours to obtain the hydrogen-type ZSM-5 molecular sieve Z-10.
Catalyst D-7 was prepared from Z-10 by the method of example 1, step (2).
Test example 1
The molecular sieves prepared in examples 1 to 6 and comparative example were tested for average crystal grain size and XRD test and SEM test, respectively. The XRD diffraction pattern of each molecular sieve is shown in figure 1, and the SEM electron micrograph of each molecular sieve is shown in figure 2.
Wherein, the average grain size of the ZSM-5 molecular sieve is tested by using a Hitachi S-4800 type scanning electron microscope;
XRD testing of ZSM-5 molecular sieves was performed on a D5005 diffractometer manufactured by Seimens, germany;
SEM pictures of ZSM-5 molecular sieves were carried out by a scanning electron microscope model Hitachi S-4800.
Z-1 molecular sieve: the average grain size was 0.8. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-1 (011), (020), (332), (051) crystal planes, respectively.
Z-2 molecular sieve: the average grain size was 0.75. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-2 (011), (020), (332), (051) crystal planes, respectively.
Z-3 molecular sieves: the average grain size was 0.95. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-3 (011), (020), (332), (051) crystal planes, respectively.
Z-4 molecular sieve: the average grain size was 0.98. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-4 (011), (020), (332), (051) crystal planes, respectively.
Z-5 molecular sieve: the average grain size was 1.1. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-5 (011), (020), (332), (051) crystal planes, respectively.
Z-6 molecular sieve: the average grain size was 1.0. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-6 (011), (020), (332), (051) crystal planes, respectively.
In FIG. 1, the XRD spectra of the Z-1 to Z-6 molecular sieves have stable baseline and no impurity peak, which indicates that the hydrogen ZSM-5 molecular sieves with good crystallinity are synthesized.
Z-7 molecular sieve: na (Na) 2 O molar content 0.92% and average grain size 2.5. Mu.m. Also at 2θ=7.9°,8.Strong diffraction peaks appear at 8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of Na-type ZSM-5, which represent the Na-type ZSM-5 molecular sieves (011), (020), (332), (051) crystal planes, respectively.
Z-8 molecular sieve: na (Na) 2 The molar content of O was 1.58% and the average grain size was 4.5. Mu.m. Also strong diffraction peaks occur at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of Na-type ZSM-5, which represent Na-type ZSM-5 molecular sieves (011), (020), (332), (051) crystal planes, respectively.
Z-9 molecular sieve: na (Na) 2 The molar content of O was 2.46%, and the average grain size was 6.3. Mu.m. Also strong diffraction peaks occur at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of Na-type ZSM-5, which represent Na-type ZSM-5 molecular sieves (011), (020), (332), (051) crystal planes, respectively.
In FIG. 1, the XRD spectra of the Z-7 to Z-9 molecular sieves have stable base lines and no impurity peaks, which indicates that the sodium ZSM-5 molecular sieves with good crystallinity are synthesized.
Z-10 molecular sieves: the average grain size was 2.3. Mu.m. Strong diffraction peaks appear at 2θ=7.9°,8.8 °,23.1 ° and 23.3 °, these diffraction peaks being typical characteristic peaks of hydrogen form ZSM-5, which represent the Z-10 (011), (020), (332), (051) crystal planes, respectively.
Test example 2
The performance of the catalysts prepared in examples 1 to 6 and comparative examples 1 to 7 was tested as follows:
in a reactor of a fixed bed mini-type evaluation apparatus, 0.5 g of a catalyst was charged, and catalyst evaluation was performed using an industrial xylene isomerization raw material. Reaction conditions: the temperature is 370 ℃, the pressure is 0.7MPa, and the feeding mass airspeed is 10h -1 The hydrogen/hydrocarbon molar ratio was 1.5. The xylene isomerization raw material composition used in the reaction is shown in table 1, the characteristics of the molecular sieve used in the catalyst of each example and the reaction result are shown in table 2, and the characteristics of the molecular sieve used in the catalyst of each comparative example and the reaction result are shown in table 3.
Isomerization activity was characterized by the isomerization rate of PX (the ratio of the amount of PX in the product to the total amount of three xylenes in the product) and catalytic selectivity was characterized by the single pass xylene yield, xy.
The catalyst performance evaluation index is calculated according to the following method:
isomerization activity:
xylene yield:
TABLE 1 composition of raw materials
Table 2 test results of examples 1 to 6
Table 3 test results of comparative examples 1 to 7
As can be seen from the results in the table, comparing the data of examples 1 to 6 and comparative examples 1 to 7, the catalyst prepared in the examples of the present invention can obtain higher isomerization activity and xylene yield when used in xylene isomerization reaction. Comparing the data of example 1 with comparative example 2, example 3 with comparative example 4, and example 5 with comparative example 6, it is clear that an isomerization catalyst having higher isomerization activity and xylene yield can be obtained by using a raw material or additive without sodium during the molecular sieve synthesis. As can be seen from comparison of the data in example 1 with comparative example 1, example 3 with comparative example 3, and example 5 with comparative example 5, the catalyst prepared from the hydrogen-type ZSM-5 molecular sieve synthesized by the one-step method of the present invention has stronger isomerization activity, isomerization selectivity and xylene yield compared with the catalyst prepared from the hydrogen-type molecular sieve obtained by the subsequent ion exchange required in the comparative example. As can be seen from the comparison of the data of example 1 and comparative example 7, the catalyst prepared from the hydrogen-type ZSM-5 molecular sieve synthesized by the method of the invention has higher isomerization activity and xylene yield.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (11)
1. A process for preparing a hydrogen form of a ZSM-5 molecular sieve, the process comprising: mixing a silicon source, an aluminum source, a template agent and water to obtain a molecular sieve synthesized mixed material; crystallizing the molecular sieve synthesized mixture at 140-190 ℃ under autogenous pressure for 40-140 hours, collecting solids and drying;
in the molecular sieve synthesis mixture, siO 2 /Al 2 O 3 The molar ratio of (2) is 20-180, the template agent: water: siO (SiO) 2 The molar ratio of (2) is 0.2-1: 10 to 60:1, wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting; the template agent is selected from quaternary ammonium base and/or quaternary ammonium salt.
2. The method according to claim 1, characterized in thatThe method also comprises the following steps: the molecular sieve synthesis mixture further comprises a pH regulator, wherein the pH regulator is combined with SiO 2 The molar ratio of the pH regulator is 0.22 to 1.5, and the pH regulator is NH 3 ·H 2 O and/or NH 4 Cl。
3. The method of claim 1, wherein the templating agent has the general formula N (R) 4 X, wherein R is selected from alkyl with 1-4 carbon atoms, and X is hydroxide ion, chloride ion or bromide ion;
in the molecular sieve synthesis mixture, the template agent and SiO 2 The molar ratio of (2) is 0.3-1.
4. The method according to claim 1, wherein in the mixture, the SiO 2 /Al 2 O 3 The molar ratio of water/SiO is 25-110 2 The molar ratio of (2) is 10-40.
5. The method of claim 1, wherein the silicon source is a silica sol and/or a silica gel; siO in the silica sol 2 The content of (2) is 10-40% by mass; the particle size of the silica gel is 0.005-0.05 mu m;
the aluminum source is aluminum nitrate and/or aluminum sulfate.
6. The method according to claim 1, wherein the crystallization treatment is carried out at a temperature of 160-185 ℃; the crystallization treatment time is 90-130 h.
7. The process according to claim 1, wherein the hydrogen form ZSM-5 molecular sieve has an average grain size of 0.05 to 10 μm.
8. A hydrogen form ZSM-5 molecular sieve prepared by the method of any one of claims 1 to 7.
9. A xylene isomerization catalyst comprising a support and platinum supported on the support; the carrier comprises 20 to 90 mass% of alumina and 10 to 80 mass% of hydrogen-form ZSM-5 molecular sieve according to claim 8, wherein the content of platinum is 0.01 to 0.6 mass% based on the carrier.
10. A method of preparing the xylene isomerization catalyst of claim 9, the method comprising:
mixing the hydrogen-type ZSM-5 molecular sieve of claim 8 with pseudo-boehmite, adding an acid solution, kneading, forming, drying and roasting to obtain a carrier, impregnating the carrier with a platinum-containing compound solution, and drying the impregnated solid at 100-140 ℃ for 8-24 h; then roasting for 2-24 h in air atmosphere at 520-550 ℃; and then reducing with hydrogen at 400-550 ℃.
11. The method of claim 10, wherein the platinum-containing compound is chloroplatinic acid.
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