WO2020019276A1 - 一种用于乙醇和苯制备乙苯的催化剂及其制备和应用 - Google Patents
一种用于乙醇和苯制备乙苯的催化剂及其制备和应用 Download PDFInfo
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- WO2020019276A1 WO2020019276A1 PCT/CN2018/097323 CN2018097323W WO2020019276A1 WO 2020019276 A1 WO2020019276 A1 WO 2020019276A1 CN 2018097323 W CN2018097323 W CN 2018097323W WO 2020019276 A1 WO2020019276 A1 WO 2020019276A1
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- molecular sieve
- catalyst
- tnu
- mesoporous
- ethanol
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 147
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 118
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 41
- 230000029936 alkylation Effects 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 29
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 239000012046 mixed solvent Substances 0.000 claims description 20
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 229910001220 stainless steel Inorganic materials 0.000 description 19
- 239000010935 stainless steel Substances 0.000 description 19
- 238000012546 transfer Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BXRYRWZWFZOCRW-UHFFFAOYSA-N butane 1-methylpyrrole Chemical compound CCCC.CN1C=CC=C1 BXRYRWZWFZOCRW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Definitions
- the invention relates to a catalyst which can be applied to the gas-phase alkylation reaction of ethanol and benzene to prepare ethylbenzene, and a preparation method and application thereof.
- Ethylbenzene is an important basic organic raw material in industry. It is mainly used for catalytic dehydrogenation to produce styrene, and then used in the field of polymer materials to prepare rubber and plastics. With the rapid development of the social economy, the market demand and production capacity of ethylbenzene have shown a clear upward trend. Data show that from 1998 to 2015, the annual growth rate of global ethylbenzene demand was 3.7%, and China's annual growth rate reached 5.3%, from 800kt in 1998 to 2Mt in 2015.
- AlCl 3 liquid phase alkyl method has simple process, mild operating conditions, and high ethylene conversion, but it has problems such as equipment corrosion, environmental pollution, and high maintenance costs.
- the molecular sieve alkylation method mainly includes the gas phase alkylation of ZSM-5 molecular sieve produced by Mobil and Badger to ethylbenzene (US3751504, US3751506, US4016218, and US4547605) and the liquid-phase alkylation of Beta and Y-type molecular sieves developed by UOP and Lummus companies.
- Techniques for the production of ethylbenzene US4891458, US5227558 and ZL02151177). These methods have the advantages of no corrosion, no pollution, simple process, high heat energy recovery and utilization.
- the process of ethanol to ethylbenzene is based on the simultaneous ethanol dehydration and alkylation of ethylene and benzene in the reactor.
- the catalyst used not only needs to meet the high dehydration selectivity and conversion of ethanol, but also has certain requirements for the catalytic efficiency of the alkylation of ethylene and benzene.
- China Petroleum and Chemical Corporation uses ZSM-5, adding a binder and modifying with rare earth oxides or alkaline earth metal oxides to obtain a series of catalysts. The treated catalyst was used in the reaction of ethylbenzene production.
- the yield of benzene is more than 80% (Chemical Reaction Engineering and Technology, 2006, 22, 172-175).
- the Italian company Versalis uses the BEA group of zeolites as a catalyst to catalyze the alkylation of bioethanol and benzene (WO2011077240).
- Patent WO2010143043 proposes the use of MTW zeolites as a catalyst, ethanol obtained by fermenting biomass-derived sugars as an alkylating agent, and alkylation reaction with benzene to generate ethylbenzene, which greatly improves the economic type of the reaction.
- MTW zeolites as a catalyst
- ethanol obtained by fermenting biomass-derived sugars as an alkylating agent
- alkylation reaction with benzene to generate ethylbenzene
- MOFs such as Fe-based MIL-110 and Al-Li-doped MIL-53
- reaction conditions 17.0 ° C
- benzene and Ethylbenzene is produced by alkylation of ethanol with a selectivity greater than 75%
- This research provides a new scheme for the selection of reaction catalysts and control of reaction conditions, but there is still a long way to go before industrialization implementation, so currently molecular sieve catalysts are still the core.
- the invention relates to a catalyst with high activity and stability for gas phase alkylation of ethanol and benzene to prepare ethylbenzene and a preparation method thereof.
- the catalyst used in the invention is a mesoporous-microporous composite Structure of TNU-9 molecular sieve.
- the present invention mainly solves the hydrothermal resistance, high alkylation activity and ethyl selectivity of the catalyst.
- the detailed preparation method of the catalyst is: using silicon oxide containing mesoporous structure, MCM-48 or SBA-15 as a silicon source, 1,4-MPB as a template, and hydrothermal synthesis to synthesize TNU-9 molecular sieve.
- the catalyst is used in the alkylation reaction of ethanol and benzene at a reaction temperature of 300 to 500 ° C, a reaction pressure of 0.1 to 2 MPa, a feed mass space velocity of 3 to 8 h -1 , and a phenyl alcohol ratio of 3 to 7 in a reaction environment.
- the main product For ethylbenzene and water.
- the catalyst of the present invention can be used stably for a long time in the reaction process of one-step gas phase alkylation of ethanol and benzene to prepare ethylbenzene, and maintain good benzene and ethanol alkylation reaction performance.
- the invention adopts a hydrothermally synthesized three-dimensional TNU-9 molecular sieve containing a meso-microporous composite structure and a ten-membered ring cross structure, and is used for the process of preparing ethylbenzene by one-step gas phase alkylation of ethanol and benzene.
- the catalyst not only has high alkylation activity and high ethyl selectivity, but also has certain hydrothermal stability and stable catalytic reaction performance.
- the patent invention provides a new catalyst for the reaction of ethanol and benzene in the preparation of ethylbenzene, and has a good application prospect.
- a catalyst for gas phase alkylation of ethanol and benzene to prepare ethylbenzene is provided.
- the catalyst has high alkylation reaction activity and ethyl selectivity in alkylation products for the reaction. High and high resistance to hydrothermal stability and stable reaction performance.
- the mesoporous-microporous composite TNU-9 molecular sieve has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 50-200.
- the upper limit of the silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of the mesoporous-microporous TNU-9 molecular sieve is selected from 200, 190, 180, 170, 160, 150, 140, 130, 120 , 110, or 100; the lower limit is selected from 100, 95, 90, 85, 80, 75, 72, 70, 68, 65, 64, 63, 60, 58, 56, 55, 52, or 50.
- the mesoporous-microporous composite TNU-9 molecular sieve has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 50-100.
- the mesoporous-microporous composite TNU-9 molecular sieve has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 60-100.
- the mesoporous-microporous composite TNU-9 molecular sieve has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 60-80.
- the mesoporous-microporous composite TNU-9 molecular sieve contains a microporous and mesoporous channel structure; and the size of the mesoporous channel is 3-50 nm.
- the mesoporous-microporous composite TNU-9 molecular sieve is a grain pile; the size of a single grain is 100-1000 nm.
- the mesoporous-microporous composite TNU-9 molecular sieve contains pores with a pore diameter of 0.3-0.8 nm.
- the mesoporous-microporous composite TNU-9 molecular sieve contains micropores with a pore diameter of 0.4-0.7 nm.
- the mesoporous-microporous TNU-9 molecular sieve contains mesopores with a pore diameter of 6-13 nm.
- the mesoporous-microporous composite TNU-9 molecular sieve contains mesopores with an upper limit selected from 13nm, 12nm, 11nm or 10nm; a lower limit selected from 9nm, 8nm, 7nm or 6nm.
- the catalyst is a high-silicon TNU-9 molecular sieve containing meso-microporous composites, the size of the mesoporous channels of the molecular sieve is 3-50 nm, and the molar ratio of silicon to aluminum of the molecular sieve SiO 2 / Al 2 O 3 is 50-200,
- the catalyst is a small-grained aggregate with a single grain size of 100-1000 nm.
- the molecular sieve is catalyzed for the reaction between ethanol and benzene to prepare ethylbenzene.
- a method for preparing a catalyst for one-step gas phase alkylation of ethanol to prepare ethylbenzene is provided.
- the method is simple, reliable, and convenient for industrial production.
- step (3) The product obtained in step (3) is calcined to obtain the molecular sieve catalyst.
- the molar ratio of the aluminum source, the alkali source, the mesoporous structure-containing silicon source, and the templating agent described in step (1) satisfies:
- SiO 2 : Al 2 O 3 : M 2 O: R: H 2 O 5 ⁇ 100: 1: 1 ⁇ 30: 5 ⁇ 20: 1000 ⁇ 4000;
- R is a templating agent, based on the number of moles of the templating agent itself;
- the number of moles of the aluminum source is the number of moles of Al 2 O 3 ;
- the number of moles of the alkali source is the number of moles of its corresponding alkali metal oxide M 2 O
- the number of moles of the silicon source is the number of moles of SiO 2 ;
- the number of moles of water is the number of moles of H 2 O itself.
- the template agent in step (1) includes at least one of 1,4-MPB, glucose, and activated carbon.
- the method for preparing 1,4-MPB includes:
- the solution containing 1,4-dibromobutane and N-methyltetrahydropyrrole is: obtaining 4-dibromobutane and N-methyltetrahydropyrrole in acetone;
- the reflux is refluxed in a water bath at 30 to 80 ° C;
- the recrystallization solvent includes a mixed solvent of methanol and ether; wherein the volume ratio of methanol and ether is 0.05-50: 1-20;
- the drying conditions are: 60 to 120 ° C for 5 to 20 hours.
- the reflux time of the water bath is 6 to 48 hours.
- the silicon source containing a mesoporous structure in step (1) is selected from at least one of silicon oxide containing a mesoporous structure, MCM-48, and SBA-15.
- the aluminum source in step (1) is selected from at least one of sodium metaaluminate, aluminum powder, aluminum nitrate, and aluminum hydroxide;
- the alkali source is selected from at least one of sodium hydroxide and potassium hydroxide.
- the stirring time in step (1) is 5 to 24 hours.
- the hydrothermal crystallization in step (2) is hydrothermal dynamic crystallization
- the hydrothermal dynamic crystallization conditions are: dynamic crystallization for 100-360h under hydrothermal conditions at 120-260 ° C.
- the upper limit of the crystallization temperature is selected from 260 ° C, 240 ° C, 220 ° C, 200 ° C, 180 ° C, 160 ° C, or 140 ° C; the lower limit is selected from 140 ° C, 130 ° C, or 120 ° C.
- the upper limit of the crystallization time is selected from 360h, 340h, 300h, or 280h; the lower limit is selected from 280h, 260h, 240h, 200h, 180h, 160h, 140h, 120h, or 100h.
- the dynamic crystallization in step (2) is rotary crystallization, and the rotation speed is 5 to 30 rpm.
- the upper limit of the rotation speed is selected from 30 rpm, 25 rpm, 20 rpm, or 15 rpm
- the lower limit is selected from 15 rpm, 10 rpm, or 5 rpm.
- the baking temperature in step (4) is 200-600 ° C, and the baking time is 1-20 hours.
- the upper limit of the baking temperature is selected from 600 ° C, 580 ° C, 550 ° C, 520 ° C, 500 ° C, or 450 ° C; the lower limit is selected from 450 ° C, 400 ° C, 300 ° C, or 200 ° C.
- the upper limit of the roasting time is selected from 20h, 18h, 15h, 12h or 10h; the lower limit is selected from 10h, 8h, 5h, 3h or 1h.
- step (3) includes: filtering and washing the product obtained in step (2) until the washing solution becomes neutral, and drying treatment at 60 to 110 ° C.
- the method includes:
- the method includes:
- the template obtained in step 1 is dissolved in water, and then an aluminum source, an alkali, and a silicon source containing a mesoporous structure are sequentially added.
- Each substance is calculated as SiO 2 , Al 2 O 3 , M 2 O, R, and H 2 O.
- the time of the reflow treatment in step 1 is 6 to 48 hours;
- the aluminum source is any one or more mixed aluminum sources of sodium metaaluminate, aluminum powder, aluminum nitrate, and aluminum hydroxide;
- the base is any one or two mixtures of sodium hydroxide and potassium hydroxide ;
- the silicon source used in step 2 is any one or two mixed silicon sources of silicon oxide containing mesoporous structure, MCM-48 or SBA-15;
- step 2 a rotary crystallization with a motor linkage is used, and the rotation speed is 5-30 rpm;
- the catalyst is prepared by using ethanol to prepare ethylbenzene.
- the evaluation conditions are: the catalyst is packed in the reaction tube of the fixed-bed reactor for reaction evaluation, the raw materials are benzene and ethanol, and the molar ratio of benzene and ethanol is 3-7: 1; the space-time space velocity of the feed weight is 3-8h -1
- the reaction temperature is 300 to 500 ° C, and the reaction pressure is 0.1 to 2 MPa.
- the above molecular sieve catalyst and the molecular sieve catalyst prepared by the above method are used for the reaction of gas phase alkylation of ethanol and benzene to prepare ethylbenzene.
- a method for preparing ethylbenzene by gas-phase alkylation of ethanol and benzene is provided, which is characterized in that:
- the raw materials containing benzene and ethanol are reacted through a fixed-bed reactor containing a catalyst to obtain the ethylbenzene;
- the catalyst includes at least one of the above molecular sieve catalyst and the molecular sieve catalyst prepared by the above method.
- the temperature of the reaction is 300 to 500 ° C
- the pressure of the reaction is 0.1 to 2 MPa
- the molar ratio of benzene to ethanol in the raw materials is 3 to 7: 1
- the space velocity is 3 ⁇ 8h -1 .
- the catalyst is at least one of the above-mentioned catalyst and the catalyst prepared by the above-mentioned method.
- the selectivity of the ethyl group is greater than 93%.
- MCM-48 molecular sieve is a M41S series mesoporous molecular sieve, which has a uniform pore size of about 2.6 nm and two sets of independent three-dimensional spiral channel network structures.
- SBA-15 molecular sieve is a mesoporous molecular sieve belonging to the P3mm space group. It has mesopores with a two-dimensional hexagonal through-hole structure.
- 1,4-MPB is short for 1,4-bis (N-methylpyrrole) butane.
- the catalyst provided in this application can efficiently convert ethanol to generate ethylbenzene in one step, simplify the process, save equipment investment, and reduce production costs;
- the catalyst provided in this application is applied to the process of gas phase alkylation of ethanol and benzene to prepare ethylbenzene. Compared with the prior art, the catalyst has improved hydrothermal stability and ethyl selectivity in the product.
- the evaluation results show that The selectivity of ethyl group is greater than 93% under the reaction conditions of a molar ratio of benzene / ethanol of 4 to 7: 1, 350 to 470 ° C and a weight space velocity of 4 to 8 h -1 ;
- the catalyst provided by this application has high resistance to hydrothermal stability and catalytic reaction stability.
- the molecular sieve is calcined at 650 ° C, and the relative crystallinity is reduced by about 15%.
- the relative crystallinity is decreased when the saturated steam treatment is conducted at 800 ° C. Only about 30%.
- the catalyst has a good application prospect and high application value.
- Figure 1 shows the topological structure of TNU-9 molecular sieve.
- FIG. 2 is an XRD pattern of the TNU-9 catalyst before reaction in Example 1.
- FIG. 2 is an XRD pattern of the TNU-9 catalyst before reaction in Example 1.
- FIG. 3 is a SEM image before the reaction of the TNU-9 catalyst in Example 1.
- FIG. 4 is a SEM image of the TNU-9 catalyst before reaction in Example 1.
- FIG. 4 is a SEM image of the TNU-9 catalyst before reaction in Example 1.
- Fig. 5 shows the conversion rate of benzene in the reaction for the gas phase alkylation reaction of ethanol and benzene to prepare ethylbenzene in Example 1.
- FIG. 6 is the ethylbenzene selectivity of the catalyst used in the ethanol to ethylbenzene reaction in Example 1.
- Silica containing mesoporous structure was purchased from Nankai University Molecular Sieve Co., Ltd., and its mesoporous pore size was 15nm.
- MCM-48 molecular sieve was purchased from Nankai University Molecular Sieve Co., Ltd., and its silicon to aluminum ratio was 30.
- SBA-15 molecular sieve was purchased from Nankai University Molecular Sieve Co., Ltd., and its silicon to aluminum ratio was 40.
- the X'pert-Pro type X-ray diffractometer of PANAnalytical Company in the Netherlands was used for XRD structure analysis.
- the Panalytical Epsilon 5 energy dispersive X-ray fluorescence spectrometer ED-XRF was used for the silicon-aluminum ratio test.
- Micromeritics ASAP-2010 type physical adsorption instrument was used for pore structure test.
- ethanol, benzene conversion and ethylbenzene selectivity are calculated based on the number of moles of carbon.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 60; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 50; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 56; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon-to-aluminum ratio of 75; micropores of 0.55 nm and mesopores of 6 nm.
- 1,4-MPB template was dissolved in 150ml of water, then 0.14g of aluminum powder, 3.6g of sodium hydroxide, and 20g of mesoporous silica material were added in sequence, and the solution was stirred for 10 hours to form a gel and filled into 200ml of stainless steel.
- hydrothermal crystallization was performed at 160 ° C for 240h, and the rotation speed was 10 rpm; the obtained product was filtered and washed until the washing solution became neutral, and the filtered cake was transferred to an oven at 80 ° C. Medium drying treatment for 12h; then the sample was baked in a 500 ° C muffle furnace for 6h to obtain a TNU-9 molecular sieve.
- the TNU-9 molecular sieve has a silicon-to-aluminum ratio of 60; micropores of 0.55 nm and mesopores of 10 nm.
- 1,4-MPB template 21.5g was dissolved in 150ml of water, then 0.14g of aluminum powder, 3.6g of sodium hydroxide and 20g of mesoporous silicon oxide material were added in order, and the solution was stirred for 10 hours to form a gel and filled into 200ml of stainless steel
- hydrothermal crystallization was performed at 160 ° C for 240h, and the rotation speed was 10 rpm; the obtained product was filtered and washed until the washing solution became neutral, and the filtered cake was transferred to an oven at 80 ° C.
- Medium drying treatment for 12h then the sample was baked in a 500 ° C muffle furnace for 6h to obtain a TNU-9 molecular sieve.
- the TNU-9 molecular sieve has a silicon-to-aluminum ratio of 60; micropores of 0.55 nm and mesopores of 13 nm.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 50; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon-to-aluminum ratio of 63; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 65; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon-aluminum ratio of 58; micropores of 0.55 nm and mesopores of 6 nm.
- TNU-9 molecular sieve has a silicon-aluminum ratio of 52; micropores of 0.55 nm and mesopores of 7 nm.
- TNU-9 molecular sieve has a silicon-aluminum ratio of 56; micropores of 0.55 nm and mesopores of 10 nm.
- TNU-9 molecular sieve has a silicon-aluminum ratio of 64; micropores of 0.55 nm and mesopores of 9 nm.
- TNU-9 molecular sieve has a silicon to aluminum ratio of 70; micropores of 0.55 nm and mesopores of 8 nm.
- TNU-9 molecular sieve has a silicon-aluminum ratio of 68; micropores of 0.55 nm and mesopores of 10 nm.
- Example 2 The operation was the same as in Example 1, except that the solution was stirred vigorously for 5 hours to form a gel and was charged into a 200 ml stainless steel reaction kettle.
- Example 2 The operation was the same as in Example 1, except that the solution was stirred vigorously for 24 hours to form a gel and was charged into a 200 ml stainless steel reaction kettle.
- Example 2 The operation is the same as in Example 1, except that the hydrothermal crystallization is performed at 120 ° C.
- Example 2 The operation is the same as in Example 1, except that the hydrothermal crystallization is performed at 260 ° C.
- Example 2 The operation was the same as in Example 1, except that the hydrothermal crystallization was performed for 100 hours.
- Example 2 The operation is the same as in Example 1, except that the sample is fired in a 200 ° C muffle furnace.
- Example 2 The operation was the same as in Example 1, except that the samples were fired in a muffle furnace at 600 ° C.
- Example 2 The operation was the same as in Example 1, except that the sample was baked in a muffle furnace for 1 h.
- Example 2 The operation is the same as in Example 1, except that the sample is baked in a muffle furnace for 20 hours.
- the TNU-9 molecular sieves obtained in Examples 1 to 25 were characterized by XRD.
- a typical XRD pattern is shown in FIG. 2, which corresponds to Example 1.
- the TNU-9 molecular sieves obtained in Examples 1 to 25 were characterized by SEM testing. Typical SEM spectra are shown in FIGS. 3 and 4, corresponding to Example 1. The SEM spectrum shows that the molecular sieve is a small-grained aggregate with a single crystal grain size of 100-1000 nm, and the small crystal grains have an irregular morphology or a flaky structure with a thickness of about 20 nm.
- the SEM images of other samples are similar to those in Fig. 3 and Fig. 4.
- the morphology of the other samples is small particles or flaky grains with a single grain size of 100-1000 nm.
- the reaction performance is shown in Figure 5 and Figure 6.
- Figure 5 shows that within a reaction time of 0-12 hours, the conversion rate of benzene is above 22%, and the conversion rate remains basically unchanged.
- Figure 6 shows that the selectivity of ethylbenzene is above 92% within a reaction time of 0-12 hours, and the selectivity remains substantially unchanged.
- Figures 5 and 6 show that the catalyst is stable and strong, has excellent catalytic effect, high conversion of reactants, and high selectivity of target products.
- the catalysts in Examples 1 to 25 were charged in a reaction tube of a fixed-bed reaction bed for reaction evaluation.
- the reaction results of Examples 1 to 16 are shown in Table 1.
- Table 1 shows that the molecular sieve catalysts prepared in Examples 1 to 16 of the present application catalyze the gas-phase alkylation of ethanol and benzene.
- the conversion rate of ethanol is more than 99%, the conversion rate of benzene is more than 15%, and the choice of ethylbenzene. Sex is above 98%.
- the TNU-9 molecular sieve catalyst prepared in the present application achieved almost the same activity as Comparative Example 1 and Comparative Example 2.
- Table 1 that the xylene content of the by-product of the TNU-9 molecular sieve catalyst prepared in the present application for catalyzing the gas-phase alkylation reaction of ethanol and benzene is as low as 540 ppm, compared to Comparative Examples 1 and 2
- the xylene content is above 850 ppm, and the product prepared by the catalyst of the present application has higher purity.
- the reaction evaluation test conditions were the same as those in Example 28.
- the catalytic reaction results are shown in Table 1.
- the reaction evaluation test conditions were the same as those in Example 28.
- the catalytic reaction results are shown in Table 1.
- the xylene content is the relative content of xylene relative to ethylbenzene in the product
- TNU-9 molecular sieve catalyst obtained in Examples 1 to 25, and the nano ZSM-5 molecular sieve catalyst in Comparative Examples 1 and 2 were subjected to a hydrothermal stability test.
- the catalyst was taken and calcined at 650 ° C for 4 hours, and the relative crystallinity of the calcined catalyst was measured.
- the experimental results show that the relative crystallinity of the TNU-9 molecular sieve catalyst obtained in Examples 1 to 25 is reduced by about 15%; the relative crystallinity of the nano-ZSM-5 molecular sieve catalyst in Comparative Examples 1 and 2 is reduced by about 16.
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Abstract
Description
Claims (23)
- 一种分子筛催化剂,其特征在于,包含介孔-微孔复合的TNU-9分子筛;所述介孔-微孔复合的TNU-9分子筛的硅铝摩尔比SiO 2/Al 2O 3为50~200。
- 根据权利要求1所述的催化剂,其特征在于,所述介孔-微孔复合的TNU-9分子筛的硅铝摩尔比SiO 2/Al 2O 3为50~100。
- 根据权利要求1所述的催化剂,其特征在于,所述介孔-微孔复合的TNU-9分子筛的硅铝摩尔比SiO 2/Al 2O 3为60~100。
- 根据权利要求1所述的催化剂,其特征在于,所述介孔-微孔复合的TNU-9分子筛的硅铝摩尔比SiO 2/Al 2O 3为60~80。
- 根据权利要求1所述的催化剂,其特征在于,所述介孔孔道尺寸为3~50nm。
- 根据权利要求1所述的催化剂,其特征在于,所述介孔-微孔复合的TNU-9分子筛为晶粒堆积体;单个所述晶粒的尺寸为100~1000nm。
- 权利要求1至6任一项所述分子筛催化剂的制备方法,其特征在于,包括以下步骤:(1)将铝源、碱源、含介孔结构的硅源加入到含有模板剂的水溶液中,搅拌,获得凝胶状前驱体;(2)将步骤(1)中获得的凝胶状前驱体水热晶化;(3)将步骤(2)中获得的产物洗涤至中性、干燥;(4)将步骤(3)中获得的产物焙烧,得到所述分子筛催化剂。
- 根据权利要求7所述的方法,其特征在于,步骤(1)中所述铝源、碱源、含介孔结构的硅源和模板剂的摩尔比满足:SiO 2:Al 2O 3:M 2O:R:H 2O=5~100:1:1~30:5~20:1000~4000;其中,R为模板剂,以模板剂自身的摩尔数计;铝源的摩尔数以Al 2O 3的摩尔数计; 碱源的摩尔数以其相应的碱金属氧化物M 2O的摩尔数计;硅源的摩尔数以SiO 2的摩尔数计;水的摩尔数以H 2O自身的摩尔数计。
- 根据权利要求7所述的方法,其特征在于,步骤(1)中所述模板剂包括1,4-MPB、葡萄糖、活性炭中的至少一种。
- 根据权利要求9所述的方法,其特征在于,所述1,4-MPB的制备方法包括:将含有1,4-二溴丁烷、N-甲基四氢吡咯的溶液回流,重结晶,干燥,得到1,4-MPB。
- 根据权利要求10所述的方法,其特征在于,所述含有1,4-二溴丁烷、N-甲基四氢吡咯的溶液为:将4-二溴丁烷、N-甲基四氢吡咯置于丙酮中获得;所述回流为30~80℃水浴回流;所述重结晶之前采用丙酮抽提;所述重结晶的溶剂包括甲醇-乙醚的混合溶剂;其中,甲醇和乙醚的体积比为0.05~50:1~20;所述干燥的条件为:60~120℃处理5~20h。
- 根据权利要求11所述的方法,其特征在于,所述水浴回流的时间为6~48h。
- 根据权利要求7所述的方法,其特征在于,步骤(1)中所述含介孔结构的硅源选自含有介孔结构的氧化硅、MCM-48、SBA-15中的至少一种。
- 根据权利要求7所述的方法,其特征在于,步骤(1)中所述铝源选自偏铝酸钠、铝粉、硝酸铝、氢氧化铝中的至少一种;所述碱源选自氢氧化钠、氢氧化钾中的至少一种。
- 根据权利要求7所述的方法,其特征在于,步骤(1)中所述搅拌的时间为5~24h。
- 根据权利要求7所述的方法,其特征在于,步骤(2)中所述水热晶化为水热动态晶化;所述水热动态晶化的条件为:120~260℃的水热条件下动态晶化100~360h。
- 根据权利要求16所述的方法,其特征在于,步骤(2)中所述动态晶化为旋转式晶化,旋转速度为5~30转/分。
- 根据权利要求7所述的方法,其特征在于,步骤(3)包括:将步骤(2)中获得的产物经过滤洗涤至洗液呈中性,60~110℃干燥处理。
- 根据权利要求7所述的方法,其特征在于,步骤(4)中所述焙烧的温度为200~600℃,所述焙烧的时间为1~20h。
- 根据权利要求7所述的方法,其特征在于,所述方法包括:1)1,4-MPB模板剂R的合成将1,4-二溴丁烷、N-甲基四氢吡咯溶于丙酮中,加热至30~80℃,回流6~48h;反应液用丙酮抽提,得到的产物用甲醇-乙醚混合溶剂进行重结晶;重结晶后的产物于60~120℃的真空干燥箱中干燥处理5~20h,得到所述模板剂R;2)TNU-9分子筛的制备将步骤1)中得到的模板剂R溶解于水中,随后依次加入铝源、碱源以及含介孔结构的硅源,得到溶液I;溶液I中各物质的摩尔比为SiO 2:Al 2O 3:M 2O:R:H 2O=5~100:1:1~30:5~20:1000~4000;将所述溶液I搅拌5~24h后形成凝胶状,装入反应釜中,在120~260℃下,电机带动的动态水热条件下晶化100~360h;将得到的产物进行过滤洗涤处理至洗液呈中性,过滤后的滤饼于60~110℃干燥处理;然后于200~600℃焙烧1~20h,即得到所述分子筛催化剂。
- 权利要求1至6任一项所述的分子筛催化剂、根据权利要求7至20任一项所述的方法制备得到的分子筛催化剂用于乙醇与苯气相烷基化制备乙苯的反应。
- 一种乙醇与苯气相烷基化制备乙苯的方法,其特征在于,含有苯和乙醇的原料通过含有催化剂的固定床反应器进行反应,得到所述乙苯;所述催化剂包括权利要求1至6任一项所述的分子筛催化剂、权利要求7至20任一项所述的方法制备的分子筛催化剂中的至少一种。
- 根据权利要求22所述的乙醇与苯气相烷基化制备乙苯的方法,其特征在于,所述反应的温度为300~500℃,所述反应的压力为0.1~2MPa;所述原料中苯与乙醇的摩尔比为3~7:1;所述原料的进料重量时空空速为3~8h -1。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/262,677 US11434183B2 (en) | 2018-07-23 | 2018-07-27 | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
BR112021001226-5A BR112021001226B1 (pt) | 2018-07-23 | 2018-07-27 | Catalisador para produzir etilbenzeno a partir de etanol e benzeno,seu método de preparo e uso |
JP2021504290A JP7154377B2 (ja) | 2018-07-23 | 2018-07-27 | エタノールとベンゼンからエチルベンゼンを製造するための触媒、その製造方法及び応用 |
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CN115591572A (zh) * | 2022-10-26 | 2023-01-13 | 陕西延长石油(集团)有限责任公司(Cn) | 一种用于乙醇和苯制乙苯的催化剂的制备方法与应用 |
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CN115501903B (zh) * | 2021-06-23 | 2024-03-29 | 中国石油化工股份有限公司 | 一种石墨烯/zsm-5分子筛复合物及其合成方法和应用 |
CN115591572A (zh) * | 2022-10-26 | 2023-01-13 | 陕西延长石油(集团)有限责任公司(Cn) | 一种用于乙醇和苯制乙苯的催化剂的制备方法与应用 |
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