CN113731478A - Zn-ZSM-5/ZSM-11 catalyst, preparation method thereof and method for producing aromatic hydrocarbon - Google Patents
Zn-ZSM-5/ZSM-11 catalyst, preparation method thereof and method for producing aromatic hydrocarbon Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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 11
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 129
- 238000005899 aromatization reaction Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 20
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 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 description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 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 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 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 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims 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 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002808 molecular sieve Substances 0.000 description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 44
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- 239000011148 porous material Substances 0.000 description 12
- 238000005216 hydrothermal crystallization Methods 0.000 description 11
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- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 239000012452 mother liquor Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- B01J35/60—
-
- B01J35/69—
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
Abstract
The invention provides a Zn-ZSM-5/ZSM-11 catalyst, a preparation method thereof and a method for producing aromatic hydrocarbon. The preparation method of the Zn-ZSM-5/ZSM-11 catalyst comprises the following steps: (1) adding a silicon source and an alkali raw material into water to obtain a mixed solution A; (2) adding an aluminum source, a template agent and a zinc source into the mixed solution A, and refluxing the reaction system at 80-150 ℃ for 2-8 hours to obtain a mixed solution B; (3) carrying out crystallization reaction on the mixed solution B at the temperature of 130-170 ℃ for 18-96 hours to obtain a mixed solution C; (4) cooling the mixed solution C to room temperature, filtering, washing and drying, and then carrying out first roasting treatment on the obtained solid product to obtain a catalyst precursor; (5) and performing ammonium exchange on the catalyst precursor, and performing second roasting treatment on an exchange product to obtain the Zn-ZSM-5/ZSM-11 catalyst. The method can prepare the Zn-ZSM-5/ZSM-11 catalyst with good catalytic performance, and has the advantages of simple process, high efficiency and the like.
Description
Technical Field
The invention relates to a Zn-ZSM-5/ZSM-11 catalyst, a preparation method thereof and a method for producing aromatic hydrocarbon.
Background
Aromatic hydrocarbons are used as important basic chemical raw materials, the demand is continuously increased, more than 85% of the aromatic hydrocarbons in China come from the production process of petroleum routes, and the aromatic hydrocarbon preparation technology is rapidly developed.
Light hydrocarbons (such as reformed topped oil, raffinate oil and the like generated in the petroleum processing process) are used as byproducts of oil refineries, have low added value and are generally used as raw materials for producing ethylene and propylene, but the utilization of the light hydrocarbons is limited to a certain degree along with the lightening of cracking raw materials, so that the application value of the light hydrocarbons is difficult to exert, and a light hydrocarbon aromatization technology provides a way for the comprehensive utilization of the light hydrocarbons. In recent years, along with the rapid development of coal chemical industry, the yield of methanol is increased rapidly, and the corresponding research on methanol aromatization technology is favored by a plurality of researchers, however, the methanol aromatization reaction belongs to a strong exothermic reaction, so that the catalyst is easy to deposit carbon and deactivate, and how to overcome the rapid accumulation of heat in the reaction process and prolong the service life of the catalyst becomes a problem which needs to be solved. Therefore, the technology for preparing the aromatic hydrocarbon by coupling the methanol with the light hydrocarbon by combining the petroleum route and the coal chemical industry has good development prospect, the same catalyst is used for catalyzing aromatization coupling reaction of the methanol and the light hydrocarbon (the light hydrocarbon is added in the methanol aromatization reaction process for aromatization coupling reaction), and heat coupling is used for making the reaction process mild, prolonging the service life of the catalyst, simultaneously improving the product yield and the aromatic hydrocarbon selectivity, and the method has important significance for the actual production of the aromatic hydrocarbon.
In 1972, Mobil corporation first developed a ZSM-5 molecular sieve belonging TO the group of high-silicon pentasil-type zeolites, the basic structural unit of which was TO4(T is Si or Al atom) tetrahedron which is composed of eight five-membered rings and has two kinds of straight cylindrical and Z-shaped transverse pore channels, and the ZSM-5 molecular sieve is widely applied to various fields of petrochemical industry by the unique pore channel structure, controllability, ion exchange property, thermal stability and excellent catalytic performance; the ZSM-11 molecular sieve which is another member in the Pentasil family was developed by the American Mobil company in the last 70 th century, the ZSM-11 belongs to a tetragonal system and is formed by three-dimensionally intersecting ten-membered ring straight-shaped channels which are parallel to the a-axis direction and the b-axis direction and have the channel size of
Compared with a complex Zig-Zag pore channel of ZSM-5, the specific straight pore channel structure of ZSM-11 ensures that the diffusion distance is shorter, reactants and products can more easily enter and exit the ZSM-11 pore channel, the diffusion rate is higher, and the possibility of side reaction is reduced, so that ZSM-11 shows better catalytic performance in a plurality of reactions.
The ZSM-5/ZSM-11 eutectic molecular sieve is a novel zeolite molecular sieve having intermediate structures of ZSM-5 and ZSM-11, which was also first disclosed by Mobil corporation of America in 1980 (US 4229424). At present, few researches and reports about ZSM-5/ZSM-11 eutectic molecular sieves exist, and the structure and performance of the eutectic molecular sieves are improved, and the optimization and application of a synthetic method are still basically explored. Chinese patent CN104624226B discloses a ZSM-5 and ZSM-11 eutectic molecular sieve andthe preparation method and the application of the molecular sieve are as follows: (1) adding an aluminum source, partial alkali and ZSM-5 seed crystal into deionized water, and stirring the mixed solution at the constant temperature of 0-30 ℃ for 2-25 hours to obtain working solution 1; (2) uniformly mixing an organic template agent, partial alkali and deionized water to obtain a working solution 2; (3) under the condition of continuous stirring, adding the working solution 2 into the working solution 1, and preparing mixed glue until the mixed glue is uniformly mixed; (4) stirring the mixed glue for 0.1-5h, adding a silicon source into the mixed glue, stirring uniformly at a constant temperature of 20-25 ℃, and stirring for 2-5 h; (5) the reaction kettle is placed into a drying oven with the temperature of 110-; (6) quickly cooling the crystallized material to room temperature, separating the solid from the mother liquor, washing the solid with deionized water until the pH value is 8-9, and drying the washed solid at 100 ℃ for 10 hours to obtain the ZSM-5/ZSM-11 eutectic molecular sieve; wherein, the molar ratio of each raw material is as follows: al (Al)2O3：(60-700)SiO2：(0.08-0.18)TBA+：(0.5-5Wt％)Seeds：(10-20)H2And O. The ZSM-5/ZSM-11 eutectic molecular sieve disclosed by the scheme is used for catalyzing methanol and/or dimethyl ether to prepare propylene, and in an implementation result, the conversion rate of the methanol is 100%, the yield of the low-carbon olefin is maintained at 55-58%, the yield of the propylene is 48%, and the P/E ratio is 9.
The zinc element (Zn) is beneficial to aromatization function, and the introduction of the zinc element into some molecular sieves can enable the molecular sieves to show catalytic effect on aromatization reaction to a certain extent, but the traditional Zn introduction mode is basically a step of firstly preparing the molecular sieves and then loading the zinc element, the preparation process is complex, and the prepared catalyst has limited catalytic performance. At present, a one-step in-situ synthesis of a Zn-loaded ZSM-5/ZSM-11 eutectic molecular sieve catalyst (Zn-ZSM-5/ZSM-11 catalyst) and an aromatization reaction for catalyzing methanol-coupled light hydrocarbon by using the catalyst are not reported, and the optimization of a synthesis process and the development of a novel aromatization catalyst are important subjects faced by technical personnel in the field in order to broaden the catalyst used for the methanol-coupled light hydrocarbon aromatization reaction, solve the series problems of harsh aromatization reaction conditions, easy carbon deposition and inactivation of the catalyst, low product yield/poor selectivity and the like at the present stage and optimize the synthesis process.
Disclosure of Invention
The invention provides a preparation method of a Zn-ZSM-5/ZSM-11 catalyst, the method adopts a one-step method to synthesize the Zn-ZSM-5/ZSM-11 catalyst in situ, the preparation process is simple, and the prepared Zn-ZSM-5/ZSM-11 catalyst has good catalytic activity and other properties.
The invention also provides a Zn-ZSM-5/ZSM-11 catalyst which has good catalytic activity and other performances and can effectively catalyze the aromatization coupling reaction of methanol and light hydrocarbon.
The invention also provides a method for producing the aromatic hydrocarbon, which realizes aromatization coupling reaction of methanol and light hydrocarbon and has higher product yield and aromatic hydrocarbon selectivity.
In one aspect of the present invention, there is provided a method for preparing a Zn-ZSM-5/ZSM-11 catalyst, comprising:
(1) adding a silicon source and an alkali raw material into water to obtain a mixed solution A;
(2) adding an aluminum source, a template agent and a zinc source into the mixed solution A, and refluxing the reaction system at 80-150 ℃ for 2-8 hours to obtain a mixed solution B;
(3) carrying out crystallization reaction on the mixed solution B at the temperature of 130-170 ℃ for 18-96 hours to obtain a mixed solution C;
(4) cooling the mixed solution C to room temperature, filtering, washing and drying, and then carrying out first roasting treatment on the obtained solid product to obtain a catalyst precursor;
(5) performing ammonium exchange on the catalyst precursor, and performing second roasting treatment on an exchange product to obtain a Zn-ZSM-5/ZSM-11 catalyst;
wherein, the adding amount of the silicon source, the alkali raw material, the aluminum source, the template agent, the zinc source and the water is controlled to meet the following molar ratio: SiO 22：Na2O：Al2O3: template agent: zn: h2O＝(30-190)：(2.0-15.0)：1.0：(0.30-5.00)：(0.5-8.0)：(1200-4000)。
The catalyst prepared by the preparation method provided by the invention is a multi-stage pore (containing micropores (the pore diameter is less than 2 mu m), mesopores (the pore diameter is 2-50 mu m) and macropores (the pore diameter is more than 50 mu m)) Zn-ZSM-5/ZSM-11 catalyst (Zn-loaded multi-stage pore ZSM-5/ZSM-11 eutectic molecular sieve catalyst), the catalyst is synthesized in situ by adopting a one-step method, the preparation process is simple, the efficiency is high, and the catalyst has excellent performances such as good catalytic activity and the like, which are specifically shown in the following steps: the catalyst can effectively catalyze aromatization coupling reaction of methanol and light hydrocarbon raw materials (such as reforming topped oil, raffinate oil and the like), is not easy to deposit carbon and deactivate in the reaction process, has longer service life, and can simultaneously enable the reaction to achieve higher liquid yield and aromatic selectivity.
In one embodiment of the present invention, the amounts of the silicon source, the alkali raw material, the aluminum source, the template, the zinc source, and the water added may be controlled to satisfy the following molar ratios: SiO 22：Na2O：Al2O3: template agent: zn: h2O ═ 40-175: (3.0-10.0): 1.0: (0.3-2.5): (1.5-4.0): (1600-3600) is beneficial to preparing the Zn-ZSM-5/ZSM-11 catalyst and enables the catalyst to have more excellent catalytic performance.
Specifically, in the implementation process of the present invention, in step (1), a silicon source and an alkali raw material may be generally added into water, and stirred at 10-50 ℃ for 2-10 hours to obtain a mixed solution a, and the operation conditions may enable the silicon source and the alkali raw material to be dispersed and uniformly mixed, which is more beneficial to prepare the Zn-ZSM-5/ZSM-11 catalyst with the above excellent performance. The stirring temperature can be further 20-30 ℃ and the stirring time can be further 2-5 hours or 3-5 hours by comprehensively considering the factors such as catalyst performance, reaction efficiency and the like.
Further, in the step (2), an aluminum source, a template agent and a zinc source are added into the mixed solution A, and the mixture can be stirred uniformly at 10-50 ℃ and then the reaction system is refluxed, so that the raw materials are fully contacted and reacted, and in the specific operation, the stirring time can be generally 2-6 hours. For example, in one embodiment of the present invention, the aluminum source, the templating agent, and the zinc source are added to the mixed solution a, and the mixture is stirred at 20 to 45 ℃ or 20 to 30 ℃, and the stirring time may be 2 to 4 hours.
In addition, the invention can further optimize the following conditions to be beneficial to synthesizing the Zn-ZSM-5/ZSM-11 catalyst with excellent performance: in the step (2), the reaction system can be refluxed for 2 to 5 hours at a temperature of between 90 and 120 ℃ to obtain a mixed solution B; and/or, in the step (3), the mixed solution B is subjected to crystallization reaction at 140-170 ℃ for 18-72 hours, and further subjected to crystallization reaction at 150-170 ℃ for 20-36 hours to obtain the mixed solution C.
In the present invention, the silicon source may be at least one selected from the group consisting of silica sol, silica gel and ethyl orthosilicate, and/or the alkali material may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and calcium hydroxide. Generally, the silicon source and the alkali raw material can be directly added into water for mixed reaction, or the silicon source and the aqueous solution containing the alkali raw material can be added into water for mixed reaction.
Further, the aluminum source may be selected from at least one of aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, aluminum hydroxide, and/or the templating agent may be selected from at least one of tetrabutylammonium hydroxide, tetrabutylammonium bromide, n-hexylamine, and/or the zinc source may be selected from at least one of zinc nitrate, zinc chloride, and zinc sulfate.
In general, in step (4), cooling the mixture C to room temperature, filtering, washing the filter cake, optionally controlling the pH to 8-9, and then drying to obtain the solid product; wherein the drying temperature can be 80-120 deg.C, and the drying time can be 4-8 hr.
Specifically, in the present invention, the catalyst precursor obtained in step (4) is a Zn-NaZSM-5/ZSM-11 molecular sieve (i.e., a Zn-loaded sodium-type ZSM-5/ZSM-11 eutectic molecular sieve), and in specific implementation, the first calcination treatment may generally include: heating the solid product to 500-550 ℃ and roasting for 4-6 hours to obtain a catalyst precursor; wherein the heating rate is controlled to be 1-5 deg.C/min, and further 2-3 deg.C/min.
The catalyst precursor is ammonium exchanged to realize the conversion from sodium form to hydrogen form, and in the specific implementation process of the present invention, ammonium salt solution may be used for ammonium exchange, the concentration of the ammonium salt solution may be 0.5-1mol/L, the ammonium exchange temperature may be 70-90 deg.c, and the ammonium exchange time may be 2-6 hr. The ammonium salt may be an ammonium salt commonly used in the art, and may include ammonium nitrate, ammonium chloride, and the like.
After the ammonium exchange, the exchange product can generally be dried first, for example at 80-120 ℃ for 4-8 hours. In the specific operation, the ammonium exchange and drying steps can be generally carried out 1 to 3 times, and then the exchanged product is subjected to a second roasting treatment.
After ammonium exchange and second roasting treatment, a Zn-HZSM-5/ZSM-11 molecular sieve catalyst (i.e., a Zn-loaded hydrogen-type ZSM-5/ZSM-11 eutectic molecular sieve) is prepared, and specifically, in the implementation process of the present invention, the second roasting treatment may generally include: heating the exchange product to 500-550 ℃ and roasting for 4-6h to obtain the Zn-ZSM-5/ZSM-11 catalyst; wherein the heating rate is controlled to be 1-5 deg.C/min, and further 2-3 deg.C/min.
In general, the molecular sieve may be further processed by molding, for example, mixing the molecular sieve with an auxiliary agent such as a binder, and then extruding the mixture into a strip, so as to facilitate the use of the molecular sieve, and in an embodiment of the present invention, the method may further include: after the exchange product is subjected to second roasting treatment, mixing the second roasting treatment product with a binder for forming, drying the formed product at 80-120 ℃ for 4-8 hours, and roasting at 500-550 ℃ for 4-6 hours to obtain a Zn-ZSM-5/ZSM-11 catalyst product; wherein, the binder can be pseudo-boehmite and/or silica sol, and the mass ratio of the second roasting treatment product to the binder can be 7: (2-4), for example, 7: 3.
In another aspect of the present invention, there is provided a Zn-ZSM-5/ZSM-11 catalyst prepared by the above-mentioned preparation method.
The catalyst is a Zn-loaded multi-stage pore ZSM-5/ZSM-11 eutectic molecular sieve catalyst, has excellent performances such as high catalytic activity and the like, can effectively catalyze aromatization coupling reaction of methanol and light hydrocarbon raw materials through tests, improves reaction efficiency, liquid yield and aromatic selectivity, is not easy to deposit carbon and inactivate in the reaction process, and has longer service life.
In still another aspect of the present invention, there is provided a method for producing aromatic hydrocarbons, comprising: the Zn-ZSM-5/ZSM-11 catalyst is adopted to catalyze the aromatization reaction of methanol and light hydrocarbon raw materials to obtain aromatic hydrocarbon products.
Specifically, the aromatization reaction conditions may generally be: the temperature is 300-500 deg.C, and further can be 350-450 deg.C, such as 400 deg.C, and the pressure is 0.1-1MPaIf the pressure can be 0.5MPa, the feeding mass space velocity is 1.0-2.0h-1For example, it may be 1.5h-1(ii) a The mass ratio of the methanol to the light hydrocarbon raw material can be generally 1:9-9:1 (i.e. the mass ratio of the methanol to the light hydrocarbon raw material is 10 parts), for example, 5: 5. The light hydrocarbon raw material may generally include reformed topping oil, raffinate oil, or other lighter hydrocarbon raw materials, such as one or a mixture of several of alkanes below C10, cycloalkanes, and the like.
Tests show that the method for producing the aromatic hydrocarbon can generally achieve more than 85 percent of liquid yield and more than 40 percent of aromatic hydrocarbon selectivity.
In the implementation process of the present invention, the aromatization reaction can be generally performed in a fixed bed reactor, and in the specific implementation, the materials to be reacted (methanol and light hydrocarbon raw materials) and the diluent gas can be mixed and enter the fixed bed reactor filled with the catalyst for aromatization reaction, wherein the flow rate of the diluent gas can be controlled to be 15-25ml/min, for example, 20 ml/min. The diluent gas used in the present invention is not particularly limited, and may be a diluent gas commonly used in the art, such as nitrogen (N)2) And the like.
The implementation of the invention has at least the following beneficial effects:
the preparation method of the Zn-ZSM-5/ZSM-11 catalyst provided by the invention adopts an in-situ hydrothermal crystallization method to synthesize the multi-level pore Zn-ZSM-5/ZSM-11 eutectic molecular sieve catalyst in one step, has the advantages of simple preparation process, high efficiency and the like, and the prepared catalyst has good catalytic activity and other properties.
The Zn-ZSM-5/ZSM-11 catalyst provided by the invention has excellent performances such as high catalytic activity and the like, can effectively catalyze aromatization coupling reaction of methanol and light hydrocarbon raw materials, and improves the liquid yield and the aromatic selectivity.
The method for producing the aromatic hydrocarbon provided by the invention has the advantages that the Zn-ZSM-5/ZSM-11 catalyst is adopted to catalyze aromatization coupling reaction of methanol and light hydrocarbon raw materials to prepare the aromatic hydrocarbon product, the reaction condition is mild, higher liquid yield and aromatic hydrocarbon selectivity can be achieved, and the technical problems of harsh aromatization reaction condition, easy carbon deposition and inactivation of the catalyst, low product yield/poor selectivity and the like in the prior art can be effectively solved.
Drawings
FIG. 1 is an XRD spectrum of Zn-ZSM-5/ZSM-11 prepared in the present invention;
FIG. 2 is the N of Zn-ZSM-5/ZSM-11 prepared by the present invention2Adsorption and desorption graphs with adsorption Volume (Volume) on the ordinate and relative pressure (P/P) on the abscissa0)。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat1)
Adding 100g of silica sol and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 2 hours at 25 ℃ to obtain a mixed solution A1;
5ml of a 1.2mol/L aluminum sulfate solution, 1.54g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A1, and the mixture was stirred at 25 ℃ for 2 hours and then refluxed at 90 ℃ for 4 hours to obtain a mixed solution B1(SiO 1)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 83.3: 4.0: 1.0: 0.98: 1.54: 1851) (ii) a
Transferring the mixed solution B1 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C1;
cooling the mixed solution C1 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
soaking a Zn-NaZSM-5/ZSM-11 molecular sieve in 1mol/L ammonium chloride solution, exchanging for 2h at 85 ℃, filtering, washing, drying for 6h at 100 ℃ after filtering and washing, repeating the exchanging, filtering, washing and drying processes for three times (namely, performing the exchanging, filtering, washing and drying processes for 3 times), placing the obtained exchange product in a muffle furnace, heating to 550 ℃ from room temperature at the rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-HZSM-5/ZSM-11 molecular sieve;
mixing a Zn-HZSM-5/ZSM-11 molecular sieve and pseudo-boehmite according to the weight ratio of 7:3 (mass ratio), extruding and molding, drying the molded product at 100 ℃ for 6h, and roasting at 550 ℃ for 4h to obtain the Zn-ZSM-5/ZSM-11 catalyst which is marked as cat 1.
2. Aromatization reaction
The method adopts cat1 as a catalyst to carry out aromatization coupling reaction of methanol and raffinate oil in a fixed bed reactor, and the reaction conditions are as follows: the mass ratio of the methanol to the raffinate oil is 5:5, the reaction temperature is 400 ℃, the pressure is 0.5MPa, the nitrogen flow rate is 20ml/min, and the total feeding mass space velocity is 1.5h-1(ii) a After 48h of reaction, a sample was taken for analysis.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 89.51% and the selectivity of aromatic hydrocarbon is 49.31%.
In the following examples 2 to 10, the conditions of the ammonium exchange to obtain the Zn-ZSM-5/ZSM-11 catalyst were the same as in example 1 unless otherwise specified, and thus the description thereof was omitted.
Example 2
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat2)
Adding 210g of silica sol and 15ml of 4mol/L sodium hydroxide solution into 180g of deionized water, and stirring for 3 hours at 25 ℃ to obtain a mixed solution A2;
5ml of a 1.2mol/L aluminum sulfate solution, 2.86g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A2, and the mixture was stirred at 30 ℃ for 3.5 hours and then refluxed at 90 ℃ for 4 hours to obtain a mixed solution B2(SiO 2)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 175.0: 5.0: 1.0: 1.84: 1.54: 1666.7);
transferring the mixed solution B2 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C2;
cooling the mixed solution C2 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 2.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat2 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 87.67%, and the selectivity of aromatic hydrocarbon is 44.26%.
Example 3
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat3)
Adding 48g of silica sol and 9ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 3 hours at 25 ℃ to obtain a mixed solution A3;
5ml of a 1.2mol/L aluminum sulfate solution, 1.47g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A3, and the mixture was stirred at 45 ℃ for 3.5 hours and then refluxed at 100 ℃ for 5 hours to obtain a mixed solution B3(SiO 3)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 40.0: 3.0: 1.0: 0.94: 1.54: 1851) (ii) a
Transferring the mixed solution B3 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C3;
cooling the mixed solution C3 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 3.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat3 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 90.12% and the selectivity of aromatic hydrocarbon is 52.68%.
Example 4
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat4)
Adding 100g of silica sol and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 4 hours at 25 ℃ to obtain a mixed solution A4;
5ml of a 1.2mol/L aluminum sulfate solution, 2.54g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A4, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 3 hours to obtain a mixed solution B4(SiO 4)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 83.3: 4.0: 1.0: 1.63: 1.54: 1851) (ii) a
Transferring the mixed solution B4 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 170 ℃ for 24 hours to obtain a mixed solution C4;
cooling the mixed solution C4 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 4.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat4 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 88.35%, and the selectivity of aromatic hydrocarbon is 46.47%.
Example 5
1. Preparation of aromatic catalyst (cat5)
Adding 100g of silica sol and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring at 25 ℃ for 2.5h to obtain a mixed solution A5;
5ml of a 1.2mol/L aluminum sulfate solution, 2.54g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A5, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 3 hours to obtain a mixed solution B5(SiO 5)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 83.3: 4.0: 1.0: 1.63: 1.54: 1851) (ii) a
Transferring the mixed solution B5 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization for 72h at 140 ℃ to obtain mixed solution C5;
cooling the mixed solution C5 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 5.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat5 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 89.62%, and the selectivity of aromatic hydrocarbon is 47.83%.
Example 6
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat6)
Adding 100g of silica sol and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 4 hours at 25 ℃ to obtain a mixed solution A6;
5ml of a 1.2mol/L aluminum sulfate solution, 3.54g of tetrabutylammonium hydroxide and 4.15g of zinc nitrate were added to the above-mentioned mixed solution A6, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 3 hours to obtain a mixed solution B6(SiO 6)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 83.3: 4.0: 1.0: 2.27: 2.3: 1851) (ii) a
Transferring the mixed solution B6 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C6;
cooling the mixed solution C6 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 6.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat6 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 86.23% and the selectivity of aromatic hydrocarbon is 51.16%.
Example 7
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat7)
Adding 80g of tetraethoxysilane and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 4.5 hours at 25 ℃ to obtain mixed solution A7;
5ml of 1.2mol/L aluminum sulfate solution, 1.89g of tetrabutylammonium bromide and 2.75g of zinc nitrate are added into the mixed solution A7, the mixture is stirred for 3 hours at 25 ℃, and then the mixture is refluxed for 3 hours at 90 ℃ to obtain mixed solution B7 (the adding amount of each raw material meets the requirement of SiO2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 64: 4.0: 1.0: 0.98: 1.54: 1851) (ii) a
Transferring the mixed solution B7 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C7;
cooling the mixed solution C7 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 7.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat7 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 88.12%, and the selectivity of aromatic hydrocarbon is 54.56%.
Example 8
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat8)
Adding 100g of tetraethoxysilane and 12ml of 4mol/L sodium hydroxide solution into 200g of deionized water, and stirring for 5 hours at 25 ℃ to obtain a mixed solution A8;
5ml of a 1.2mol/L aluminum sulfate solution, 0.98g of tetrabutylammonium bromide, 0.98g of tetrabutylammonium hydroxide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A8, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 3 hours to obtain a mixed solution B8 (the amounts of the respective raw materials added were SiO in the mixture)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 80: 4.0: 1.0: 1.35: 1.54: 1851) (ii) a
Transferring the mixed solution B8 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 150 ℃ for 36 hours to obtain a mixed solution C8;
cooling the mixed solution C8 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 8.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat8 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 88.97% and the selectivity of aromatic hydrocarbon is 50.52%.
Example 9
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat2)
Adding 60g of tetraethoxysilane and 12ml of 4mol/L sodium hydroxide solution into 160g of deionized water, and stirring for 3.5 hours at 25 ℃ to obtain mixed solution A9;
5ml of 1.0mol/L aluminum hydroxide solution, 1.98g of tetrabutylammonium bromide and 2.75g of zinc nitrate were added to the above-mentioned mixed solution A9, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 3 hours to obtain mixed solution B9 (the amount of each raw material added was SiO in the mixture)2：Na2O：Al2O3: template agent: zn: h2The molar ratio of O is about 115: 9.6: 1.0: 2.46: 3.70: 3556) (ii) a
Transferring the mixed solution B9 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 160 ℃ for 36h to obtain a mixed solution C9;
cooling the mixed solution C9 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 9.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat9 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 85.26%, and the selectivity of aromatic hydrocarbon is 40.38%.
Example 10
1. Preparation of Zn-ZSM-5/ZSM-11 catalyst (cat2)
Adding 100g of silica sol and 12ml of 4mol/L sodium hydroxide solution into 220g of deionized water, and stirring for 4 hours at 25 ℃ to obtain a mixed solution A10;
5ml of 1.2mol/L aluminum sulfate solution, 1.86g of tetrabutylammonium hydroxide and 3.75g of zinc nitrate were added to the above-mentioned mixed solution A10, and the mixture was stirred at 25 ℃ for 3 hours and then refluxed at 90 ℃ for 4 hours to obtain mixed solution B10 (the amounts of the respective raw materials added were SiO in the mixture)2：Na2O：Al2O3: template agent: zn: h2Mole of OThe molar ratio is about 83.3: 4.0: 1.0: 1.2: 2.1: 2037) (ii) a
Transferring the mixed solution B10 to a crystallization kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 160 ℃ for 36h to obtain a mixed solution C10;
cooling the mixed solution C10 to room temperature, filtering, washing to pH 8-9, drying at 100 ℃ for 6h, placing the obtained solid product in a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 2-3 ℃/min, and roasting for 4h to obtain the Zn-NaZSM-5/ZSM-11 molecular sieve;
after the steps of ammonium exchange, molding and the like, the Zn-ZSM-5/ZSM-11 catalyst is prepared and is marked as cat 10.
2. Aromatization reaction
The aromatization coupling reaction of methanol and raffinate oil (mass ratio of 5:5) was carried out according to the reaction conditions of example 1 by using cat10 as a catalyst, and a sample was taken for analysis after 48 hours of reaction.
The analysis results show that: the conversion rate of methanol is basically 100%, the liquid yield is 86.58%, and the selectivity of aromatic hydrocarbon is 52.08%.
XRD patterns and N of the Zn-HZSM-5/ZSM-11 molecular sieves of example 1 and example 2 were measured2The adsorption curves are respectively shown in fig. 1 and fig. 2 (the detection results of other embodiments are similar).
As can be seen from fig. 1, there are three diffraction peaks at 23 to 25 ° and the rightmost peak is weaker, while there are diffraction peaks at about 45 ° and the diffraction peaks are not significant (i.e., do not belong to one-shoulder or two-shoulder peaks), indicating that example 1 produces the eutectic molecular sieves ZSM-5 and ZSM-11 (typically, ZSM-5 has 3 significant diffraction peaks at about 23 to 25 ° 2 θ, ZSM-11 has only two diffraction peaks at about 23 to 25 ° 2 θ, ZSM-5 has significant two-shoulder peaks at about 45 ° 2 θ, ZSM-11 has one-shoulder peak at about 45 ° 2 θ, and the characteristic peaks shown in fig. 1 are diffraction peaks of the eutectic molecular sieve ZSM-5/ZSM-11).
As shown in FIG. 2, N of Zn-HZSM-5/ZSM-112Adsorption and desorption curves at relative pressure (P/P)0) Separation (i.e., hysteresis or hysteresis) occurs at about 0.6-0.9, followed by closure, and there is no apparent saturated adsorption plateau, similar to the International Union of pure and reference chemistry (IUPAC) classificationThe adsorption curve of the H3 type hysteresis loop shows that the molecular sieve contains micropores, mesopores and macropores, namely, a hierarchical pore structure.
The Zn-HZSM-5/ZSM-11 catalysts of examples 1 to 10 were further examined by ICP-OES, and the results showed that the catalysts prepared in examples 1 to 10 all contained Zn, i.e., the Zn-supported ZSM-5/ZSM-11 eutectic molecular sieve type catalysts (the ICP-OES examination results of examples 1 and 2 are shown in Table 1).
TABLE 1 ICP-OES assay results for Zn-HZSM-5/ZSM-11
| Sample (I) | Si/Al | Si(mg/g) | Al(mg/g) | Zn(mg/g) |
| Example 1 | 40.3 | 652.9 | 16.2 | 16.8 |
| Example 2 | 85.6 | 1275.4 | 14.9 | 9.8 |
The detection results show that the ZSM-5/ZSM-11 eutectic molecular sieve based catalyst loaded with Zn is synthesized in situ in the embodiments 1 to 10 by adopting a one-step method, and the aromatization test shows that the catalyst has good performances such as catalytic activity and the like, can catalyze aromatization coupling reaction of light hydrocarbon raw materials such as methanol, raffinate oil and the like, is not easy to deposit carbon and inactivate during the reaction, has long service life, and can achieve higher liquid yield and aromatic selectivity.
Claims (10)
1. A preparation method of a Zn-ZSM-5/ZSM-11 catalyst is characterized by comprising the following steps:
(1) adding a silicon source and an alkali raw material into water to obtain a mixed solution A;
(2) adding an aluminum source, a template agent and a zinc source into the mixed solution A, and refluxing the reaction system at 80-150 ℃ for 2-8 hours to obtain a mixed solution B;
(3) carrying out crystallization reaction on the mixed solution B at the temperature of 130-170 ℃ for 18-96 hours to obtain a mixed solution C;
(4) cooling the mixed solution C to room temperature, filtering, washing and drying, and then carrying out first roasting treatment on the obtained solid product to obtain a catalyst precursor;
(5) performing ammonium exchange on the catalyst precursor, and performing second roasting treatment on an exchange product to obtain a Zn-ZSM-5/ZSM-11 catalyst;
wherein, the adding amounts of the silicon source, the alkali raw material, the aluminum source, the template agent, the zinc source and the water are controlled to meet the following molar ratio: SiO 22：Na2O：Al2O3: template agent: zn: h2O＝(30-190)：(2.0-15.0)：1.0：(0.30-5.00)：(0.5-8.0)：(1200-4000)。
2. The process according to claim 1, wherein in the step (2), the reaction system is refluxed at 90 to 120 ℃ for 2 to 5 hours to obtain a mixed solution B; and/or, in the step (3), the mixed solution B is subjected to crystallization reaction at 140-170 ℃ for 18-72 hours to obtain a mixed solution C.
3. The method according to claim 1 or 2, wherein the silicon source is at least one selected from the group consisting of silica sol, silica gel, and tetraethoxysilane, and/or the alkali material is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and calcium hydroxide.
4. The method according to claim 1 or 2, wherein the aluminum source is at least one selected from the group consisting of aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, aluminum hydroxide, and/or the templating agent is at least one selected from the group consisting of tetrabutylammonium hydroxide, tetrabutylammonium bromide, n-hexylamine, and/or the zinc source is at least one selected from the group consisting of zinc nitrate, zinc chloride, and zinc sulfate.
5. The method according to any one of claims 1 to 4, characterized in that the first roasting treatment comprises: heating the solid product to 500-550 ℃ and roasting for 4-6 hours to obtain a catalyst precursor; wherein the heating rate is controlled to be 1-5 ℃/min.
6. The production method according to any one of claims 1 to 4, wherein the ammonium exchange is carried out using an ammonium salt solution having a concentration of 0.5 to 1mol/L, an ammonium exchange temperature of 70 to 90 ℃, and an ammonium exchange time of 2 to 6 hours.
7. The production method according to any one of claims 1 to 4, wherein the ammonium salt includes ammonium nitrate and ammonium chloride.
8. The method according to any one of claims 1 to 4, characterized in that the second roasting treatment comprises: heating the exchange product to 500-550 ℃ and roasting for 4-6h to obtain a Zn-ZSM-5/ZSM-11 catalyst; wherein the heating rate is controlled to be 1-5 ℃/min.
9. A Zn-ZSM-5/ZSM-11 catalyst, characterized by being prepared according to the preparation method of any of claims 1 to 8.
10. A method for producing aromatic hydrocarbons, comprising: the use of the Zn-ZSM-5/ZSM-11 catalyst of claim 8 to catalyze the aromatization of methanol and light hydrocarbon feedstocks to produce aromatics products.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745715A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of small crystal grain ZSM-5/ZSM-11 composite zeolite |
| CN103539153A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of nano hierarchical-pore ZSM-11/ZSM-5 eutectic zeolite |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105195172A (en) * | 2015-09-22 | 2015-12-30 | 西南化工研究设计院有限公司 | In-situ synthesis method for light-hydrocarbon aromatization catalyst |
-
2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745715A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of small crystal grain ZSM-5/ZSM-11 composite zeolite |
| CN103539153A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of nano hierarchical-pore ZSM-11/ZSM-5 eutectic zeolite |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105195172A (en) * | 2015-09-22 | 2015-12-30 | 西南化工研究设计院有限公司 | In-situ synthesis method for light-hydrocarbon aromatization catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CHAO SONG ET AL: "Influence of reaction conditions on the aromatization of cofeeding n-butane with methanol over the Zn loaded ZSM-5/ZSM-11 zeolite catalyst", 《FUEL PROCESSING TECHNOLOGY》, vol. 126, 10 May 2014 (2014-05-10) * |
| MARYAM JUYBAR ET AL: "Conversion of methanol to aromatics over ZSM-5/11 intergrowth Zeolites and bimetallic Zn-Cu-ZSM-5/11 and Ga-Ag-ZSM-5/11 catalysts prepared with direct synthesis method", 《JOURNAL OF CHEMICAL SCIENCES》, vol. 131, 1 November 2019 (2019-11-01), pages 2, XP036946631, DOI: 10.1007/s12039-019-1684-8 * |
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