CN114426287B - ZSM-5 molecular sieve and synthesis method thereof - Google Patents
ZSM-5 molecular sieve and synthesis method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 109
- 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 109
- 238000001308 synthesis method Methods 0.000 title claims description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 28
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 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 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 24
- 239000000243 solution Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 10
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 81
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 53
- 239000005977 Ethylene Substances 0.000 description 53
- 238000002156 mixing Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000005804 alkylation reaction Methods 0.000 description 14
- 238000000926 separation method Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical group [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001228 spectrum 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- 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
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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
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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
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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
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Abstract
The invention discloses a ZSM-5 molecular sieve, which solves the problems that the ZSM-5 molecular sieve synthesized in the prior art contains alkali metal ions and the molecular sieve is required to be exchanged for NH in the ammonium exchange process 4 -ZSM-5 problem. The acid value of the ZSM-5 molecular sieve is 95-99%, and the Na content is 0.01-0.05 wt.%; the ZSM-5 molecular sieve is synthesized by 1) contacting a raw material ZSM-5 molecular sieve with an alkali solution to obtain a mixed solution A; 2) Contacting water, an aluminum source, a silicon source, a guiding agent and the mixed solution A to obtain mixed solution B; 3) Crystallizing the mixed solution B to obtain a mixed solution C; 4) The mixed solution C is processed to obtain the ZSM-5 molecular sieve, so that the problems are well solved.
Description
Technical Field
The invention belongs to the technical field of catalytic chemistry and chemical engineering, and particularly relates to a synthesis method of a ZSM-5 molecular sieve.
Background
ZSM-5 molecular sieve was first synthesized in 1972 (US 3702886) by Mobil corporation, and is widely used in the petrochemical field due to its special double-ten-membered ring channel structure and high hydrothermal stability. Generally, a certain amount of alkali metal ion (e.g., na) is required to be added during the synthesis of ZSM-5 molecular sieve + ) The alkali metal ions play a very important role in the crystallization process of the ZSM-5 molecular sieve, and are mainly expressed in the following two aspects: firstly, the catalyst can be used as a mineralizer to provide a precursor required by crystallization of a molecular sieve; and secondly, alkali metal ions can balance negative charges of the molecular sieve framework and keep the framework electrically neutral. Typically Na + The ZSM-5 molecular sieve obtained in the presence is called Na-ZSM-5, which has no acidic catalytic active center and requires one-step ammoniumThe exchange process uses Na + Exchange to NH 4 + Obtain NH 4 ZSM-5, and then roasting to obtain the H-ZSM-5 molecular sieve with acid catalytic active center. The ammonium exchange process uses a large amount of ammonium salt, generates a large amount of high-concentration ammonia nitrogen-containing wastewater, has high environmental protection pressure, and increases the sewage treatment cost.
Alkali metal ions are not added in the crystallization process of ZSM-5 molecular sieve to directly synthesize NH 4 The ZSM-5 molecular sieve can effectively omit the ammonium exchange process, reduce the emission of ammonia nitrogen wastewater and greatly reduce the production cost. Patent CN103086399A discloses an NH 4 Firstly, mixing a silicon source and an organic template agent, and aging to obtain guide glue; then mixing water, aluminum source, alkali source, silicon source and guiding glue, crystallizing at 120-210 deg.C to obtain NH 4 -ZSM-5 molecular sieve.
Disclosure of Invention
One of the technical problems to be solved by the invention is that ZSM-5 molecular sieve synthesized in the prior art contains alkali metal ions, and the molecular sieve is exchanged for NH in the ammonium exchange process 4 -ZSM-5 problem.
The second technical problem to be solved by the invention is to provide a synthesis method of ZSM-5 molecular sieve which is one of the technical problems to be solved.
In order to solve one of the technical problems, the invention adopts the following technical scheme: providing a ZSM-5 molecular sieve, wherein the acid value of the molecular sieve is 95% -99%, and the acid value of the molecular sieve is NH 3 The ratio of the total acid amount of the molecular sieve obtained by the TPD test to the theoretical acid amount of the molecular sieve obtained by calculation, i.e. the acid value of the molecular sieve=0.03×a×b, where a is NH 3 TPD test molecular sieve total acid mmol/g, b is the SiO of the molecular sieve obtained by ICP test 2 /Al 2 O 3 (molar ratio);
wherein the theoretical acid amount of the molecular sieve is set to 60g/mol of the molecular sieve ZSM-5 according to the following method, and the SiO of the molecular sieve is tested according to ICP 2 /Al 2 O 3 The mole number of aluminum atoms in the molecular sieve is calculated to be (100/3 b) mmol/g, and the aluminum atoms are set to be framework four-coordination aluminum and are summedThe theoretical acid amount of the molecular sieve is (100/3 b) mmol/g when the protonic acid coordinates. Wherein a is 0.0317-1.65 and b is 20-1000; preferably a is 0.0396-1.1 and b is 30-800.
The Na content in the molecular sieve is 0.01wt.% to 0.05wt.%, and the Na content is preferably 0.012wt.% to 0.035wt.%.
In order to solve the second technical problem, the synthesis process of the ZSM-5 molecular sieve comprises the following steps:
1) Contacting a raw material ZSM-5 molecular sieve with an alkaline substance to obtain a mixed solution A;
2) Contacting water, an aluminum source, a silicon source, a guiding agent and the mixed solution A to obtain mixed solution B;
3) Crystallizing the mixed solution B to obtain a mixed solution C;
4) The mixed solution C is treated to obtain a ZSM-5 molecular sieve;
in order to solve the second technical problem, the ZSM-5 molecular sieve synthesis process also comprises the following steps: 1) Carrying out hydrothermal treatment on the mixed solution A; 4) And (3) separating, drying and roasting the mixed solution C.
In the above technical scheme, preferably, the raw material ZSM-5 molecular sieve refers to ZSM-5 molecular sieve obtained by a conventional method, wherein SiO 2 /Al 2 O 3 (molar ratio) of 50-2000, preferably SiO 2 /Al 2 O 3 (molar ratio) is 100-1500.
In the above technical solution, preferably, the structural formula of the alkali is
Wherein R1, R2, R3 and R4 are each any one of methyl, ethyl, propyl or isopropyl, preferably R1, R2 are propyl, R3, R4 are isopropyl; or R1 is methyl, R2 is ethyl, and R3 and R4 are propyl; or R1, R2, R3 and R4 are isopropyl; or R1 and R2 are methyl, and R3 and R4 are propyl.
According to the technical scheme, preferably, the mass concentration of the aqueous solution of the alkaline substance is 10% -50%.
In the above technical scheme, preferably, the mass ratio of the aqueous solution of the alkaline substance to the raw material ZSM-5 molecular sieve is (2-20): 1.
According to the technical scheme, preferably, the hydrothermal treatment condition of the mixed solution A is that the mixed solution A is subjected to airtight treatment at 80-170 ℃ for 0.5-24 hours.
In the above technical solution, preferably, the aluminum source is one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide or aluminum isopropoxide.
In the above technical solution, preferably, the silicon source is one or more of white carbon black, ammonium silica sol or solid silica gel.
In the above technical solution, preferably, the guiding agent is one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, n-butylamine or hexamethylenediamine.
In the above technical scheme, preferably, the molar ratio of water, aluminum source, guiding agent and silicon source in the mixed solution B is that the water to silicon source is H 2 O/SiO 2 =5-20; silicon source, aluminum source is SiO 2 /Al 2 O 3 =20-1000; guiding agent, silicon source is R/SiO 2 ＝0.1-0.4。
In the above technical scheme, preferably, the mixed solution A and the silicon source (according to pure SiO 2 Calculated) is A/SiO 2 ＝0.3-1.2。
In the above technical scheme, preferably, the crystallization condition of the mixed solution B is that the mixed solution B is subjected to closed reaction for 4-72 hours at 130-200 ℃.
NH is adopted as the total acid amount of the molecular sieve 3 The TPD method test, the temperature programming desorption device test of the type 200906PX18 of the Peng Xiang technology Co., tianjin is adopted, 0.15g sample (20-40 meshes) after tabletting is placed in a quartz U-shaped reactor with the inner diameter of 5mm, the quartz U-shaped reactor is activated for 1h under the He gas atmosphere at 550 ℃, then cooled to below 100 ℃, ammonia gas is introduced for adsorption to saturation, then the temperature is raised to 100 ℃, the temperature is raised to 1h after the He gas is purged, the temperature programming desorption is started, and the temperature is raised to 600 ℃ at the temperature raising rate of 10 ℃/min;
ICP was measured using a Model S-35 ICP-AES analyzer from Kontron, and 50mg of the sample was completely dissolved in 50g of hydrofluoric acid solution before the measurement.
The alkylation reaction method of benzene and ethylene adopts the ZSM-5 molecular sieve or the synthesis methodThe molecular sieve is prepared at the reaction temperature of 360-420 ℃, the pressure of 1.0-2.0MPa and the ethylene mass airspeed of 1.0-3.0h -1 And (3) alkylation reaction of ethylene and benzene under the condition that the molar ratio of benzene to ethylene is 4.0-5.5.
The acid value of the ZSM-5 molecular sieve synthesized by the method is 95 to 99 percent, and the Na content is 0.01 to 0.05 percent by weight; the molecular sieve does not need to carry out ammonium exchange, has an acidic catalytic active center after direct roasting, can avoid the use of a large amount of ammonium salt in the ammonium exchange process, and can avoid the generation of a large amount of ammonia nitrogen-containing wastewater, thereby effectively saving cost and relieving environmental protection pressure. The conversion rate of ethylene and the selectivity of ethyl in the alkylation reaction of benzene and ethylene are obviously improved, the pressure is 1.0-2.0MPa, and the mass space velocity of ethylene is 1.0-3.0h at the reaction temperature of 360-420 DEG C -1 The conversion rate of ethylene is 99.5-99.9% and the ethyl selectivity is 99.5-99.9% under the condition that the mole ratio of benzene to ethylene is 4.0-5.5.
Drawings
FIG. 1 is a schematic representation of NH of a ZSM-5 molecular sieve synthesized in accordance with the present invention 3 -TPD spectrum
Detailed Description
[ example 1 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: mixing 5g of commercial ZSM-5 molecular sieve and 60g of 30% alkaline substance aqueous solution (R1 and R2 are propyl groups in the alkali structural formula; R3 and R4 are isopropyl groups) uniformly, treating for 5H in a 110 ℃ closed environment to obtain a mixed solution A, and mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A uniformly to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. NH of ZSM-5 molecular sieve 3 The TPD spectrum is shown in FIG. 1, by NH 3 TPD test gives a of 0.109, ICP test gives b of 298, calculated acid number of 97.4% and Na content of the molecular sieve0.025wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.8% and the ethyl selectivity was 99.7% at a benzene to ethylene molar ratio of 4.0.
[ example 2 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: uniformly mixing 5g of commercial ZSM-5 molecular sieve and 60g of aqueous solution of alkaline substance with mass concentration of 10% (wherein R1 is methyl, R2 is ethyl, R3 and R4 are propyl in the alkali structural formula), then treating for 5H in a 110 ℃ closed environment to obtain a mixed solution A, and uniformly mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (with mass fraction of 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gives a of 0.106 and ICP test gives b of 299, calculated to give an acid number of 95.1% and Na content of 0.028wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.7% and the ethyl selectivity was 99.8% at a benzene to ethylene molar ratio of 4.0.
[ example 3 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: mixing 5g of commercial ZSM-5 molecular sieve and 60g of 50% alkaline substance aqueous solution (R1, R2, R3 and R4 are isopropyl in the alkali structural formula), treating for 5H in a 110 ℃ closed environment to obtain a mixed solution A, and mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A uniformly to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gave a of 0.110, ICP test gave b of 297, calculated to give an acid number of 98.2% and Na content of 0.018wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.8% and the ethyl selectivity was 99.8% at a benzene to ethylene molar ratio of 4.0.
[ example 4 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: mixing 5g of commercial ZSM-5 molecular sieve and 10g of 30% alkaline substance aqueous solution (R1 and R2 are methyl groups, R3 and R4 are propyl groups in the alkali structural formula), treating for 5H in a 110 ℃ closed environment to obtain a mixed solution A, and mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A uniformly to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gives a 0.105 and ICP test gives b 301, calculated to give an acid number of 95.2% and Na content of 0.026wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.6% and the ethyl selectivity was 99.8% at a benzene to ethylene molar ratio of 4.0.
[ example 5 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: 5g of commercial ZSM-5 molecular sieve and 100g of base with a mass concentration of 30%Uniformly mixing aqueous solutions of sexual substances (R1 and R2 are propyl groups in an alkali structural formula; R3 and R4 are isopropyl groups), treating for 5 hours in a closed environment at 110 ℃ to obtain a mixed solution A, and uniformly mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gives a 0.111 and ICP test gives b 296, calculated to give an acid number of 98.5% and Na content of 0.012wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.9% and the ethyl selectivity was 99.7% at a benzene to ethylene molar ratio of 4.0.
[ example 6 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: mixing 5g of commercial ZSM-5 molecular sieve and 60g of 30% alkaline substance aqueous solution (R1 and R2 are propyl groups in the alkali structural formula; R3 and R4 are isopropyl groups) uniformly, treating for 24 hours in a sealed environment at 80 ℃ to obtain a mixed solution A, and mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A uniformly to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gave a of 0.109 and ICP test gave b of 298, calculated to give an acid number of 97.2% and Na content of 0.023wt.%. Benzene is applied to the obtained ZSM-5 molecular sieveAnd ethylene alkylation reaction, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.6% and the ethyl selectivity was 99.8% at a benzene to ethylene molar ratio of 4.0.
[ example 7 ]
The synthesis process of the ZSM-5 molecular sieve is as follows: mixing 5g of commercial ZSM-5 molecular sieve and 60g of 30% alkaline substance aqueous solution (R1 and R2 are propyl groups in the alkali structural formula; R3 and R4 are isopropyl groups) uniformly, then treating for 0.5H in a closed environment at 170 ℃ to obtain a mixed solution A, and then mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (the mass fraction is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A uniformly to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, crystallizing the mixed solution B in a closed environment at 160 ℃ for 36 hours to obtain a mixed solution C, and carrying out conventional separation, drying and other processes on the mixed solution C to obtain the ZSM-5 molecular sieve. By NH 3 TPD test gave a of 0.107 and ICP test gave b of 303, calculated to give an acid number of 97.5% and Na content of 0.021wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 99.8% and the ethyl selectivity was 99.7% at a benzene to ethylene molar ratio of 4.0.
Comparative example 1
The procedure was the same as in example 1 except that the aqueous solution of the basic substance was replaced with a tetrapropylammonium bromide solution.
The synthesis process of the ZSM-5 molecular sieve is as follows: uniformly mixing 5g of commercial ZSM-5 molecular sieve and 60g of tetrapropylammonium bromide aqueous solution with mass concentration of 30%, then treating for 5 hours in a closed environment at 110 ℃ to obtain a mixed solution A, and uniformly mixing 21.6g of water, 0.222g of aluminum sulfate, 15g of ammonium type silica sol (40 mass percent is 40%), 1.828g of n-butylamine and 3.6g of the mixed solution A to obtain a mixed solution B, wherein H 2 O/SiO 2 ＝12、SiO 2 /Al 2 O 3 ＝300、R/SiO 2 =0.25, mixed solution a and ammonium type silica sol (as pure SiO 2 Calculated) is 0.6, the mixed solution B is crystallized for 36 hours in a closed environment at 160 ℃ to obtain mixed solution C, and the mixed solution C is subjected to conventional separation, drying and other processes to obtain an amorphous material. By NH 3 TPD test gives a of 0.005, ICP test gives b of 858, calculated to give an acid number of 12.9% for the molecular sieve and Na content of 0.031wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 At a benzene to ethylene molar ratio of 4.0, the ethylene conversion was 2.3% and the ethyl selectivity was 42%.
Comparative example 2
The synthesis method refers to patent CN103086399A, firstly preparing guide adhesive A: 43.1 g of tetraethyl orthosilicate are added dropwise to 58.8 g of tetrapropylammonium hydroxide (25%), 29.8 g (SiO 2 :0.35TPAOH:25H 2 O:4 EtOH), stirring until tetraethyl orthosilicate is hydrolyzed, and aging at 80 ℃ for 3 days to obtain the guide adhesive A.
0.112 g of aluminum sulfate octadecanoate and 0.43 g of tetrapropylammonium bromide are dissolved in 5.4 g of water, added to 2.2 g of ammonia water after dissolution, added with 0.12 g of guide gum A and 10g of silica sol (30.0%), and finally added with the following components (SiO) 2 /Al 2 O 3 ＝300，NH 3 H 2 O/SiO 2 ＝0.6,R/SiO 2 ＝0.033,H 2 O/SiO 2 The amount of silica in the guide gel was 0.5% of the total amount of silica in the synthesis system, and after stirring at room temperature, the mixture was crystallized at 175 ℃ for 24 hours to give ZSM-5 molecular sieve. By NH 3 TPD test gives a of 0.098, ICP test gives b of 295, calculated to give an acid number of 86.7% and Na content of 0.06wt.%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 The ethylene conversion was 95.1% and the ethyl selectivity was 97.2% at a benzene to ethylene molar ratio of 4.0.
[ comparative example 3 ]
The synthesis method refers to patent CN104941695A, and the preparation process comprises the following steps:
step 1: 11 g of tetraethyl orthosilicate, 0.3 g of aluminum nitrate, 18 g of tetrapropylammonium hydroxide, 2g of urea, 0.2 g of potassium hydroxide and 18 g of water are mixed and stirred at normal temperature to prepare a precursor solution, then the precursor solution is transferred into a synthesis kettle, the synthesis kettle is sealed, crystallization is carried out for 48 hours at 180 ℃, after the crystallization is finished, the reaction mixture is subjected to solid-liquid separation and washing with deionized water, the solid is dried at 90 ℃ for 24 hours, and finally the solid is baked for 10 hours in an air atmosphere at 550 ℃.
Step 2: mixing and stirring the molecular sieve raw powder with 20 ml of ammonium salt solution with the concentration of 0.1mol/L for 24 hours, filtering, mixing and stirring the filter cake with the ammonium salt solution with the concentration of 0.1mol/L again for 24 hours, filtering, repeating the steps for 5 times, drying at 100 ℃ for 24 hours, and roasting at 550 ℃ for 10 hours to obtain the hydrogen ZSM-5 molecular sieve.
Step 3: mixing and stirring the molecular sieve raw powder and 9.2 ml of 0.05mol/L zinc nitrate solution, drying at 90 ℃, and roasting for 6 hours in an air atmosphere at 550 ℃ to obtain the Zn/HZSM-5 molecular sieve. By NH 3 TPD gives an M of 0.4 and N73 by ICP test, calculated as 88% acid number of the molecular sieve. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 At a benzene to ethylene molar ratio of 4.0, the ethylene conversion was 75.1% and the ethyl selectivity was 87.2%.
[ comparative example 4 ]
The synthesis method refers to patent CN104843740A, and the preparation process comprises the following steps:
step 1: homogenizing ingredients: mixing and homogenizing amorphous silica, boehmite and tetrapropylammonium hydroxide (TPAOH) to obtain a ZSM-5 molecular sieve precursor, wherein the ratio of SiO2 to Al2O3 to TPAOH (mass ratio of substances) in the precursor is 1:0.01:0.07. Step 2: and (3) assisting crystallization: placing a TPAOH solution with the concentration of 10.5wt% at the bottom of a crystallization kettle, and placing the ZSM-5 molecular sieve precursor obtained in the step 1 into the crystallization kettle without directly contacting with the TPAOH aqueous solution; the mass ratio of the precursor to the TPAOH aqueous solution is 0.1, and the temperature is raised to 190 ℃ to carry out steam assisted crystallization for 3 hours, so as to obtain a crystallized product.
Step 3: and (3) heating the crystallized product obtained in the step (2) to 550 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 5 hours to obtain the hydrogen ZSM-5 molecular sieve.
By NH 3 TPD gives an M of 0.286, N of 100 by ICP test, calculated as acid number of 85.8%. The ZSM-5 molecular sieve is applied to the alkylation reaction of benzene and ethylene, the reaction temperature is 400 ℃, the pressure is 1.5MPa, and the ethylene mass space velocity is 2.5h -1 At a benzene to ethylene molar ratio of 4.0, the ethylene conversion was 96.1% and the ethyl selectivity was 84.2%.
Table 1 conditions for synthesizing molecular sieves and parameters for obtaining samples
Claims (9)
1. The synthesis method of the ZSM-5 molecular sieve is characterized by comprising the following steps of:
1) Contacting a raw material ZSM-5 molecular sieve with an alkaline substance to obtain a mixed solution A;
2) Contacting water, an aluminum source, a silicon source, a guiding agent and the mixed solution A to obtain mixed solution B;
3) Crystallizing the mixed solution B to obtain a mixed solution C;
4) The mixed solution C is treated to obtain a ZSM-5 molecular sieve;
the structural formula of the alkaline substance is
Wherein R1, R2, R3 and R4 are each any one of methyl, ethyl, propyl or isopropyl;
the aluminum source is one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide or aluminum isopropoxide; the silicon source is one or more of white carbon black, ammonium type silica sol or solid silica gel; the guiding agent is one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, n-butylamine or hexamethylenediamine.
2. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, further comprising the steps of: 1) Carrying out hydrothermal treatment on the mixed solution A; 4) And (3) separating, drying and roasting the mixed solution C.
3. The method for synthesizing ZSM-5 molecular sieve according to claim 1, wherein the raw material ZSM-5 molecular sieve contains SiO 2 /Al 2 O 3 The molar ratio is 50-2000.
4. The method for synthesizing ZSM-5 molecular sieve according to claim 1, wherein the raw material ZSM-5 molecular sieve contains SiO 2 /Al 2 O 3 The molar ratio is 100-1500.
5. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein R1 and R2 are propyl groups, and R3 and R4 are isopropyl groups; or R1 is methyl, R2 is ethyl, and R3 and R4 are propyl; or R1, R2, R3 and R4 are isopropyl; or R1 and R2 are methyl, and R3 and R4 are propyl.
6. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein the alkaline substance is an aqueous solution of the alkaline substance, and the mass concentration of the alkaline substance is 10% -50%; the mass ratio of the aqueous solution of the alkaline substance to the ZSM-5 molecular sieve is (2-20): 1.
7. The method for synthesizing the ZSM-5 molecular sieve according to claim 2, wherein the hydrothermal treatment condition is that the closed treatment is carried out at 80-170 ℃ for 0.5-24 h.
8. The method for synthesizing ZSM-5 molecular sieve according to claim 1, wherein the molar ratios of water, aluminum source, directing agent and silicon source in the mixed solution B are respectively water to siliconThe source is H 2 O/SiO 2 =5-20; silicon source, aluminum source is SiO 2 /Al 2 O 3 =20-1000; guiding agent, silicon source is R/SiO 2 =0.1-0.4。
9. The method for synthesizing ZSM-5 molecular sieve according to claim 1, wherein the mixture A and the silicon source in the mixture B are prepared from pure SiO 2 Calculated mass ratio of A/SiO 2 =0.3-1.2; the crystallization condition of the mixed solution B is that the mixed solution is subjected to airtight reaction for 4-72 hours at 130-200 ℃.
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| DE3021580A1 (en) * | 1980-06-07 | 1981-12-24 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING ZEOLITHES AND USE THEREOF AS CATALYSTS |
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| CN104843740B (en) * | 2014-02-13 | 2017-12-12 | 中国科学院过程工程研究所 | A kind of molecular sieves of ZSM 5 and preparation method thereof |
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| CN104941695B (en) * | 2015-06-08 | 2019-01-11 | 清华大学 | A kind of nano-ZSM-5 molecular sieve catalyst and preparation, application method |
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