CN111589467A - 一种中空zsm-5分子筛催化剂的制备及应用 - Google Patents
一种中空zsm-5分子筛催化剂的制备及应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- 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 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 34
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 34
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 34
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 150000003951 lactams Chemical class 0.000 claims abstract description 5
- 239000006259 organic additive Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 5
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 38
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- 238000001354 calcination Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- -1 halogen sodium salt Chemical class 0.000 description 5
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- 150000002430 hydrocarbons Chemical class 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 208000012868 Overgrowth Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229930195712 glutamate Natural products 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C01B39/026—After-treatment
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
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- 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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Abstract
一种中空ZSM‑5分子筛催化剂的制备,属于石油化工产品的生产技术领域,其特征在于包括如下步骤:取原始摩尔组成为:SiO2/Al2O3=20‑100,Na2O/SiO2=0.1‑0.4,TPA+/SiO2=0.30‑1.0,H2O/SiO2=15‑40,R/SiO2=3‑6的硅源、铝源、无机碱、微孔模板剂、去离子水和有机添加剂内酰胺(R)均匀混合;均匀混合后进行高温动态晶化;对晶化产物进行固液分离,将固体产物经过滤、洗涤、干燥得到中空ZSM‑5分子筛。与实心ZSM‑5分子筛催化剂相比,可以把碳四烯烃催化裂解转化为乙烯和丙烯同时,提高了催化剂的反应性能。
Description
技术领域
本发明属于石油化工产品的生产技术领域,尤其涉及一种中空ZSM-5分子筛催化剂的制备及应用。
背景技术
乙烯和丙烯是重要的有机化工原料,随着国民经济的快速发展,对其需求也不断增加。除了烃类蒸汽裂解、催化裂解和甲醇制烯烃,碳四碳五烯烃催化裂解也是获得乙烯和丙烯的重要途径之一。该技术具有工艺简单,投资少和见效快的特点,受到工业界和学术界的青睐。
专利CN1611471A和CN1611472A中提出一种烯烃催化裂解生产丙烯的方法,前者用磷改性低硅铝比的ZSM-5分子筛催化剂达到提高目的产物丙烯的选择性和收率。后者以硅铝比优选范围为230-600的ZSM-5型分子筛,通过调控ZSM-5型分子筛的晶粒大小,减少反应物和生成物的停留时间以达到提高催化剂的选择性和稳定性的目的。该专利侧重于分子筛原粉的合成,并未加入其它活性组份进行改性。
专利CN1600757采用经铵离子交换后的ZSM-5/ZSM-11共结晶分子筛,用K、Mg、La和Ce调配分子筛的性能,以丁烯为原料,在500-600℃,液相空速1-50h-1和0.01-0.8MPa条件下,乙烯和丙烯的总收率达到40%-50%。催化裂解反应时间短,对催化剂的稳定性没有进行考察。
专利CN1490288在ZSM型分子筛原粉的晶化过程中添加卤素钠盐,以碳四及碳四以上烯烃为反应原料,详细地考察了分子筛在晶化过程中不同卤素钠盐与二氧化硅的配比对催化裂解反应的影响,着重于分子筛的晶化合成,对反应过程中丙烯的选择性和稳定性没有做进一步的阐述。
CN1274342A公开了通过转化含有20%(重量)或更高(以烃原料的重量计)的至少一种C4-C12烯烃的直链烃为原料制取乙烯和丙烯的方法。该方法使用的沸石催化剂中的沸石是SiO2/Al2O3摩尔比为200-5000,含有至少一种IB族金属,中等孔径的沸石,优选ZSM-5家族的沸石,反应在400-700℃,0.1-10个大气压及1-1000h-1的重量时空速下进行,使用的稀释气体包括氢气,甲烷,蒸汽和惰性气体,可获得最高到6.5%的乙烯产率和22.7%的丙烯收率,没有对稳定性做进一步阐述。
CN101927180披露了一种碳四烯烃制丙烯的催化剂:75%-95%的高硅沸石(ZRP或ZSM-5),5%-20%的氧化硅和1%-10%的改性组分(氧化钙和/或氧化锂,氧化硼或氧化磷)。该催化剂具有良好的稳定性和再生性能。
金文清等人[化学反应工程与工艺,2007,23(3):193-199]研究了丁烯在氢氧化钠处理后ZSM-5分子筛上催化裂解生产乙烯和丙烯的性能,结果表明碱处理后引入的介孔可促进丁烯催化裂解生产乙烯和丙烯。
赵国良等[催化学报,2005,26(12):1083-1087]考察了氟硅酸铵改性后分子筛催化剂上丁烯裂解性能,发现氟硅酸铵可以降低分子筛的表面酸性,在一定程度上抑制氢转移和芳构化副反应;疏通分子筛的孔道,提高了催化剂的稳定性。
CN108689788A披露了一种碳四烯烃催化裂解制备丙烯的方法,催化剂的活性组分为失活的具有MFI结构的含钛分子筛或者为失活的具有MFI结构的含钛分子筛和磷改性ZSM-5分子筛的混合物。
虽然ZSM-5分子筛应用广泛,但是由于其较小的孔径分布,使反应物分子不易接近分子筛的活性位而影响其利用率,较大的产物分子不易脱离活性位而导致副反应发生,容易导致积碳、催化效率低、催化剂快速失活等问题。为了克服微孔分子筛单一微孔结构导致的扩散限制,目前人们采用了两条途径。一是缩短分子筛的孔道长度,即合成纳米分子筛。纳米分子筛具有较短的扩散路径长度和较大的比表面积,使得其催化性能和热稳定性等发生很大变化。二是拓宽分子筛的孔道尺寸,即向微孔分子筛中引入介孔或大孔形成多级孔分子筛。多级孔分子筛可改善大分子反应物和产物的扩散性能,从而提高反应速率和目标产物的选择性。介孔分子筛中介孔孔径为20-50nm,中空分子筛中中空孔径为50-400nm;微介孔分子筛的制备比较容易,研究也较多,涉及反应也多,而中空分子筛制备比较难,涉及反应较少,主要用于封装金属然后进行催化反应。中空分子筛保持原有微孔分子筛的择形性,特别是反应物和产物尺寸较小时;另外中空分子筛的机械强度比介孔分子筛的更大。
人们发明了各种不同的合成技术,包括层层自组装(LBL)法、硬模板法、二次生长法或LBL/二次生长法等先后被用于制备中空分子筛。其中,一步合成中空ZSM-5分子筛是科研界和工业界追求的目标。
张伟等报道[RSC Advance,2018,8:31979-31983]在常规ZSM-5合成原料中通过合成条件的变化一次合成中空ZSM-5,制备成POM-MOF-ZSM-5催化剂在二苯并噻吩氧化脱硫反应中体现出优越反应性能。
车顺爱等[Chemistry-A European Journal,2019,25:6196-6202]以TPABr,Al[OCH(CH3)2]3和TEOS原料,在TPABr/SiO2>1.0,Si/Al:20-100,140℃一步合成了中空ZSM-5分子筛,没有述及任何反应。
李瑞丰等[Crystal Growth&Design,2017,17:4900-4907]报道在常规ZSM-5合成原料中添加纤维素谷氨酸钠可以一步合成中空ZSM-5分子筛,没有述及任何反应。
CN104261427B披露在无机碱源,铝源中添加适量N-甲基-2-吡咯烷酮(NMP)的结构导向剂,随后将硅源缓慢加入,一步水热合成“插卡”型的多级孔HCL-ZSM-5分子筛。该分子筛的初级结构单元为ZSM-5纳米片,片与片相互平行(片与片之间有空隙)、垂直交叉堆垛成具有方形二次孔道的三维“插卡”结构。该专利不含有机模板剂如四丙基氢氧化铵等,静态合成,得到的为多级孔(介-大孔孔径为5-80nm,集中于16nm附近),但不是中空的ZSM-5;另外,其它吡咯烷酮添加对ZSM-5的合成没有说明,最后没有述及任何反应。
发明内容
本发明旨在解决上述问题,提供一种中空ZSM-5分子筛催化剂的制备及应用。
本发明所述中空ZSM-5分子筛催化剂的制备,包括如下步骤:(1)取原始摩尔组成为:SiO2/Al2O3=20-100,Na2O/SiO2=0.1-0.4,TPA+/SiO2=0.30-1.0,H2O/SiO2=15-40,R/SiO2=3-6的硅源、铝源、无机碱、微孔模板剂、去离子水和有机添加剂内酰胺(R)均匀混合;均匀混合后进行高温动态晶化;对晶化产物进行固液分离,将固体产物经过滤、洗涤、干燥得到中空ZSM-5分子筛;
(2)将得到的中空ZSM-5分子筛烧除微孔模版剂后用氯化铵溶液交换,干燥、焙烧,制成中空H-ZSM-5分子筛催化剂。
进一步,本发明所述中空ZSM-5分子筛催化剂的制备,步骤(1)所述微孔模板剂为四丙基氢氧化铵、四丙基溴化铵中的一种或一种以上。
进一步,本发明所述中空ZSM-5分子筛催化剂的制备,步骤(1)所述有机添加剂内酰胺为2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮中的一种或一种以上。
进一步,本发明所述中空ZSM-5分子筛催化剂的制备,步骤(1)所述高温动态晶化过程为:在温度为150-180℃、旋转烘箱的转速为40-80转/分钟的状态下进行晶化40-100h,水热合成中空ZSM-5分子筛。
进一步,本发明所述中空ZSM-5分子筛催化剂的制备,步骤(2)所述氯化铵溶液的浓度为0.3-1.0mol/L;所述交换的温度为60-90℃;交换次数为1-3次。
进一步,本发明所述中空ZSM-5分子筛催化剂的制备,步骤(2)所述焙烧温度为550-750℃,焙烧时间为5-15h。
本发明所述中空ZSM-5分子筛催化剂的应用,所述中空ZSM-5分子筛催化剂用于催化裂解碳四碳五烯烃制乙烯和丙烯。
本发明有益效果:
用本发明所述中空ZSM-5分子筛催化剂的制备方法得到的催化剂,与实心ZSM-5分子筛催化剂相比,可以把碳四烯烃催化裂解转化为乙烯和丙烯同时,提高了催化剂的反应性能。
附图说明
图1为本发明所述对比例1制备的实心ZSM-5分子筛X射线衍射(XRD)谱图;
图2为本发明所述对比例1制备的实心ZSM-5分子筛透射电镜(TEM)图片;
图3为本发明所述实施例1制备的中空ZSM-5分子筛的XRD谱图;
图4为本发明所述实施例1制备的中空ZSM-5分子筛的TEM图片。
具体实施方式
下面通过附图及实施例对本发明所述中空ZSM-5分子筛催化剂的制备及应用进行详细说明。
对比例1
在搅拌条件下,将19.6g硅溶胶(25.5wt.%SiO2,74.5wt.%H2O)、1.45g硝酸铝(≥99wt.%)、0.69g氢氧化钠、31.1g四丙基氢氧化铵水溶液(TPAOH,纯度≥35wt.%)按一定顺序加入反应釜中。原料混合物的摩尔组成为:SiO2/Al2O3=43.5,Na2O/SiO2=0.1,TPA+/SiO2=0.636,H2O/SiO2=16,搅拌30min,使其充分混合均匀,将合成釜密封,直接在150℃动态(50转/分钟)晶化72h,用自来水淬灭反应,离心分离得到固体产物,然后蒸馏水洗涤,烘干,550℃焙烧5h后在80℃下用0.8mol/L的氯化铵溶液交换3次,水洗2次,120℃干燥,650℃焙烧10h,所得催化剂记作Cat-A。Cat-A的XRD谱图如图1所示,归属于MFI构型,图2给出的透射电镜(TEM)图片显示其为实心ZSM-5分子筛催化剂。
实施例1
在搅拌条件下,将19.6g硅溶胶(25.5wt.%SiO2,74.5wt.%H2O)、1.45g硝酸铝(≥99wt.%)、0.69g氢氧化钠、31.1g TPAOH水溶液,33.3g N-甲基-2吡咯烷酮(NMP)按一定顺序加入反应釜中。原料混合物的摩尔组成为:SiO2/Al2O3=43.5,Na2O/SiO2=0.1,TPA+/SiO2=0.636,NMP/SiO2=4.0,H2O/SiO2=16,搅拌30min,使其充分混合均匀,将合成釜密封,直接在150℃动态(50转/分钟)晶化72h,用自来水淬灭反应,离心分离得到固体产物,然后蒸馏水洗涤,烘干,550℃焙烧5h后在80℃下用0.8mol/L的氯化铵溶液交换3次,水洗2次,120℃干燥,650℃焙烧10h,所得催化剂记作Cat-B。Cat-B的XRD谱图如图3所示,归属于MFI构型,图4给出的TEM图片显示其为中空ZSM-5分子筛催化剂。
实施例2
在搅拌条件下,将17.4g正硅酸乙酯(≥99wt.%)、2.0g氯化铝(≥99wt.%)、2.7g氢氧化钠、10.2g四丙基溴化铵(TPABr,纯度≥35wt.%))水溶液、43g N-乙基-2吡咯烷酮(NEP)、14.5g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为:SiO2/Al2O3=20,Na2O/SiO2=0.4,TPA+/SiO2=0.3,NEP/SiO2=6.0,H2O/SiO2=30,搅拌30min,使其充分混合均匀,将合成釜密封,直接在180℃动态(80转/分钟)晶化100h,用自来水淬灭反应,离心分离得到固体产物,然后蒸馏水洗涤,烘干,500℃焙烧3h后在60℃下用1.0mol/L的氯化铵溶液交换1次,水洗2次,120℃干燥,750℃焙烧5h,所得催化剂记作Cat-C。Cat-C的XRD谱图和TEM图片分别与图3和图4类似。
实施例3
在搅拌条件下,将5.15g粗孔硅胶(97.0wt.%SiO2,3.0wt.%H2O)、0.56g硫酸铝、0.88g碳酸钠(≥99.5wt.%)、13.4gTPAOH水溶液、19.8gNMP、4.26g N-甲基-2吡咯烷酮(P,纯度≥99wt.%)、29g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为:SiO2/Al2O3=100,Na2O/SiO2=0.10,TPA+/SiO2=1.0,NMP/SiO2=2.0,P/SiO2=1.0,H2O/SiO2=40,搅拌30min,使其充分混合均匀,将合成釜密封,直接在180℃动态(40转/分钟)晶化48h,用自来水淬灭反应,离心分离得到固体产物,然后蒸馏水洗涤,烘干,540℃焙烧4h后在90℃下用0.5mol/L的氯化铵溶液交换1次,水洗2次,120℃干燥,650℃焙烧15h,所得催化剂记作Cat-D。Cat-D的XRD谱图和TEM图片分别与图3和图4类似。
实施例4
在搅拌条件下,将5.1g层析硅胶(98.0wt.%SiO2,2.0wt.%H2O)、0.15g拟薄水铝石(69wt.%SiO2,31wt.%H2O)、0.89g碳酸钠(≥99.5wt.%)、25.8g TPAOH水溶液、16.9gTPABr水溶液、25g NMP、15g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为:SiO2/Al2O3=80,Na2O/SiO2=0.1,TPA+/SiO2=0.8,NMP/SiO2=3.0,H2O/SiO2=20,搅拌30min,使其充分混合均匀,将合成釜密封,直接在160℃动态(60转/分钟)晶化80h,用自来水淬灭反应,离心分离得到固体产物,然后蒸馏水洗涤,烘干,550℃焙烧4h后在80℃下用0.6mol/L的氯化铵溶液交换2次,水洗2次,120℃干燥,700℃焙烧10h,所得催化剂记作Cat-E。Cat-E的XRD谱图和TEM图片分别与图3和图4类似。
对比例1和实施例1-4于碳四碳五烯烃混合气裂解反应评价
将对比例1和实施例1-4所得的催化剂分别置于内径为12mm连续流动的固定床反应器中上进行催化剂性能评价,催化剂的装填量为1g,在N2气氛下升温到500℃活化1h,然后在N2气氛下降到反应温度,原料为液化气(碳四烯烃:烷烃=70:30w/w,表1)或者碳四碳五烯烃混合气(碳四烯烃:碳五烯烃:烷烃=48:12:30w/w,表2),反应条件为:0.1MPa,580℃,原料重量空速20h-1。反应后的产物经冷却器冷却进行气液分离。气体和液体产物均用Agilent7890A色谱系统分析组成,液体产物采用Al2O3-S毛细管柱,氢焰检测器。分析结果归一化,得到甲烷、乙烷、丙烷、丁烷、乙烯、丙烯、丁烯、戊烯,戊烷和C6 +产物组成。本发明采用的百分数均为重量百分含量。
液化气催化裂解制乙烯和丙烯的反应结果如表1所示,在相同反应条件下,实心ZSM-5分子筛催化剂(Cat-A)上丁烯转化率低于中空ZSM-5分子筛催化剂(Cat-B),相应的乙烯+丙烯选择性也是空心催化剂(Cat-B)优于实心样品(Cat-A),Cat-B-Cat-E上丁烯转化率和低碳烯烃(乙烯,丙烯)选择性均优于Cat-A。
表1:催化剂上液化气催化裂解制乙烯和丙烯反应性能
样品 | Cat-A | Cat-B | Cat-C | Cat-D | Cat-E |
丁烯转化率 | 65.46 | 74.76 | 74.49 | 69.87 | 70.44 |
乙烯选择性 | 15.80 | 18.20 | 17.68 | 15.87 | 15.90 |
丙烯选择性 | 46.92 | 49.86 | 49.92 | 52.30 | 52.76 |
乙烯+丙烯选择性 | 62.72 | 68.06 | 67.60 | 68.17 | 68.66 |
碳五及以上产物选择性 | 27.69 | 22.43 | 24.24 | 23.72 | 23.96 |
原料:液化气(碳四烯烃:烷烃=70:30w/w)
反应条件:0.1MPa;580℃;液化气重量空速20h-1
碳四碳五烯烃混合气催化裂解制乙烯和丙烯的反应结果如表2所示,在相同反应条件下,实心ZSM-5分子筛催化剂(Cat-A)上丁烯和戊烯转化率低于中空ZSM-5分子筛催化剂(Cat-B),相应的乙烯+丙烯选择性也是空心催化剂(Cat-B)优于实心样品(Cat-A),Cat-B-Cat-E上丁烯和戊烯转化率,以及低碳烯烃(乙烯+丙烯)选择性均优于Cat-A。
表2:催化剂上碳四碳五烯烃混合气催化裂解制乙烯和丙烯反应性能
样品 | Cat-A | Cat-B | Cat-C | Cat-D | Cat-E |
丁烯转化率 | 64.07 | 73.15 | 72.70 | 68.94 | 68.84 |
戊烯转化率 | 80.04 | 85.20 | 84.85 | 83.61 | 86.91 |
乙烯选择性 | 18.23 | 20.55 | 21.35 | 18.99 | 19.49 |
丙烯选择性 | 47.28 | 47.51 | 47.90 | 50.41 | 51.60 |
乙烯+丙烯选择性 | 65.51 | 68.06 | 69.25 | 69.40 | 71.09 |
戊烷及碳六以上产物选择性 | 24.82 | 20.68 | 19.72 | 22.06 | 20.33 |
原料:碳四碳五烯烃混合气(碳四烯烃:碳五烯烃:烷烃=58:12:30w/w)
反应条件:0.1MPa;580℃;碳四碳五烯烃混合气重量空速20h-1。
上述实施例只是部分较佳实施例,并不是对本发明的限制。实际上只要是符合发明内容部分阐述的条件都可以实现本发明,因此,本发明保护范围以申请的权利要求为准。
Claims (7)
1.一种中空ZSM-5分子筛催化剂的制备,其特征在于包括如下步骤:
(1)取原始摩尔组成为:SiO2/Al2O3=20-100,Na2O/SiO2=0.1-0.4,TPA+/SiO2=0.30-1.0,H2O/SiO2=15-40,R/SiO2=3-6的硅源、铝源、无机碱、微孔模板剂、去离子水和有机添加剂内酰胺(R)均匀混合;均匀混合后进行高温动态晶化;对晶化产物进行固液分离,将固体产物经过滤、洗涤、干燥得到中空ZSM-5分子筛;
(2)将得到的中空ZSM-5分子筛烧除微孔模版剂后用氯化铵溶液交换,干燥、焙烧,制成中空H-ZSM-5分子筛催化剂。
2.根据权利要求1所述中空ZSM-5分子筛催化剂的制备,其特征在于:步骤(1)所述微孔模板剂为四丙基氢氧化铵、四丙基溴化铵中的一种或一种以上。
3.根据权利要求1所述中空ZSM-5分子筛催化剂的制备,其特征在于:步骤(1)所述有机添加剂内酰胺为2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮中的一种或一种以上。
4. 根据权利要求1所述中空ZSM-5分子筛催化剂的制备,其特征在于:步骤(1)所述高温动态晶化过程为:在温度为150-180℃、旋转烘箱的转速为40-80转/分钟的状态下进行晶化40-100 h,水热合成中空ZSM-5分子筛。
5.根据权利要求1所述中空ZSM-5分子筛催化剂的制备,其特征在于:步骤(2)所述氯化铵溶液的浓度为0.3-1.0mol/L;所述交换的温度为60-90oC;交换次数为1-3次。
6.根据权利要求1所述中空ZSM-5分子筛催化剂的制备,其特征在于:步骤(2)所述焙烧温度为550-750oC,焙烧时间为5-15 h。
7.一种根据权利要求1-6任一项所述中空ZSM-5分子筛催化剂的应用,其特征在于:所述中空ZSM-5分子筛催化剂用于催化裂解碳四碳五烯烃制乙烯和丙烯。
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