CN112657498A - Catalyst for preparing aromatic hydrocarbon from methanol and preparation method thereof - Google Patents
Catalyst for preparing aromatic hydrocarbon from methanol and preparation method thereof Download PDFInfo
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- CN112657498A CN112657498A CN201910977049.5A CN201910977049A CN112657498A CN 112657498 A CN112657498 A CN 112657498A CN 201910977049 A CN201910977049 A CN 201910977049A CN 112657498 A CN112657498 A CN 112657498A
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- aromatic hydrocarbon
- hydroxide
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000003980 solgel method Methods 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 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 5
- 239000000203 mixture Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- -1 siloxane compound Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing aromatic hydrocarbon from methanol and a preparation method thereof. The catalyst contains active components of Cu, Zn, Al and Si; the molar ratio of Cu to Zn to Al to Si = 0.01-0.1: 0.05-0.2: 1: 25-50. The method adopts a sol-gel method to prepare the catalyst, is simple and convenient, does not need to be dipped with other auxiliary agents for many times, and the prepared catalyst has the aromatic hydrocarbon yield reaching 71.2 percent and the BTX yield reaching 64.3 percent in the initial reaction stage; after 200h, the yield of the aromatic hydrocarbon still reaches 69.8%, the yield of BTX reaches 59.4%, and the method has high yield of the aromatic hydrocarbon, high yield of BTX and high stability.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing aromatic hydrocarbon from methanol and a preparation method thereof.
Background
Aromatic hydrocarbons, particularly light aromatic hydrocarbons such as benzene, toluene and xylene, are important raw materials which are in short supply in the petrochemical industry of China, and the demand is huge. At present, aromatic compounds in China mainly come from petroleum catalytic reforming and high-temperature cracking, and with the gradual depletion of petroleum resources, the preparation of aromatic hydrocarbons through a petroleum route can bring huge cost pressure to the petrochemical industry in China. On the other hand, coal resources are rich in China, and the methanol production process is mature day by day, so that a powerful raw material guarantee is provided for the production of methanol in China and even in the world, and a sufficient raw material guarantee is provided for the methanol-to-aromatics reaction (MTA). Although the MTA technology in China has made great progress, low reaction space velocity, low BTX yield and high catalyst deactivation rate are still the main reasons limiting the industrialization of the process.
Chinese patent CN1880288A discloses a process for preparing aromatic hydrocarbon by methanol conversion, a catalyst and a catalyst preparation method, wherein the catalyst takes a small-grain ZSM-5 molecular sieve as a carrier, the small-grain ZSM-5 molecular sieve is mixed with a binder, ground and roasted, and then dipped with active components gallium and lanthanum to prepare the catalyst, and the catalyst is prepared at an operating pressure of 0.1-5.0 MPa, an operating temperature of 300-460 ℃ and a raw material liquid hourly space velocity of 0.1-6.0 h-1Under the condition, the reaction product is cooled and separated, the liquid phase selectivity is more than 33 percent, and the yield of the aromatic hydrocarbon in the liquid phase is more than 60 percent.
Chinese patent CN109701598A discloses a catalyst for preparing aromatic hydrocarbon from methanol and application thereofThe agent comprises 0.5-10 parts of phosphorus element or oxide thereof, 1-15 parts of at least one element selected from group IIB of the periodic table of elements or oxide thereof, 0.001-1 part of alkaline earth metal or oxide thereof, 0.1-10 parts of copper element or oxide thereof, and 50-90 parts of silicon-aluminum molecular sieve, and the reaction temperature is 350-500 ℃, the operating pressure is 0.001-1.0 MPa, and the mass space velocity of methanol is 0.1-5.0 h-1The yield of aromatic hydrocarbon reaches 65 percent under the condition.
Chinese patent CN101780417B discloses a catalyst for preparing p-xylene and low-carbon olefin by methanol conversion, a preparation method and application thereof, the catalyst is obtained by modifying surface acidity and pore structure of a zeolite molecular sieve modified by transition metal and rare earth metal through a siloxane compound, and the methanol mass space velocity is 2.0h at the reaction temperature of 450 DEG C-1Under the reaction conditions of (3), the yield of the aromatic hydrocarbon is about 50 percent.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a catalyst for preparing aromatic hydrocarbon from methanol and a preparation method thereof, aiming at the problems of low reaction space velocity, low BTX yield, high catalyst inactivation rate and the like of an MTA catalyst in the prior art. The catalyst has the characteristics of high reaction airspeed, high BTX yield and better stability.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme.
The invention provides a catalyst for preparing aromatic hydrocarbon from methanol, which is characterized by comprising active components of Cu, Zn, Al and Si; the molar ratio of Cu to Zn to Al to Si = 0.01-0.1: 0.05-0.2: 1: 25-50; the Cu is derived from copper salt, the Zn is derived from zinc salt, the Al is derived from sodium metaaluminate or aluminum isopropoxide, and the Si is derived from silica sol or ethyl orthosilicate.
The invention also provides a preparation method of the catalyst, the catalyst is prepared in a sol-gel mode, and the preparation method comprises the following steps:
(1) dissolving copper salt, zinc salt, organic ammonium template agent, structure directing agent, aluminum source and alkali metal hydroxide in deionized water, preparing a solution after all the components are dissolved, adding a silicon source into the solution under the stirring state, and continuously stirring for 0.5-2h to obtain raw material mixture gel;
(2) controlling the temperature of the gel obtained in the step (1) at 160-200 ℃ for 24-96 h, and converting the gel into powder;
(3) washing the powder obtained in the step (2), filtering, drying, and adding NH4NO3Stirring the solution and carrying out hydrothermal treatment;
(4) and washing and drying the finally obtained solid, roasting, extruding and forming to obtain the catalyst.
Preferably, the copper salt, the zinc salt, and the nitrate salt of each of them in step (1); the organic ammonium template is selected from tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide or tetrabutyl ammonium bromide; the structure directing agent is selected from cetyl trimethyl ammonium bromide or polyethylene glycol; the alkali metal hydroxide is selected from sodium hydroxide or potassium hydroxide.
Preferably, the molar ratio of each component in the raw material mixture in the step (1) is Cu: Zn: SiO2:Al2O3The organic ammonium template is a structure directing agent, namely 0.01-0.1: 0.05-0.2: 25-50: 0.5: 0.2-0.4: 0.05-0.1: 5-10: 2000-4000 alkali metal hydroxide and deionized water.
Preferably, the gel in the step (2) is filled into a reaction kettle and put into an oven for temperature control treatment.
Preferably, the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining.
Preferably, in the step (3), the powder obtained in the step (2) is washed, filtered and dried, and then 1mol/lNH is added4NO3The solution was hydrothermally treated for 6 hours at 65 ℃ with stirring.
Preferably, in the step (4), the drying temperature is 100-120 ℃, the drying time is 24-48 hours, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours.
The invention also provides an application of the catalyst, and the catalyst is used for a reaction for preparing aromatic hydrocarbon from methanol.
Preferably, when the catalyst is used for preparing aromatic hydrocarbon from methanol, the catalyst is loaded into a fixed bed reactor, and the methanol is preheated before reaction at the preheating temperature of 130-180 ℃.
Preferably, the conditions of the catalyst used for the reaction of preparing aromatic hydrocarbon from methanol are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 0.2-1.5 MPa, and the methanol feeding flow is 0.1-0.3 ml/min.
Advantageous effects
The preparation process of the catalyst is simple and convenient, and a good catalytic effect can be obtained without an additional impregnation cocatalyst, the yield of aromatic hydrocarbon at the initial stage of reaction reaches 71.2%, and the yield of BTX reaches 64.3%; after 200h, the yield of the aromatic hydrocarbon still reaches 69.8%, the yield of BTX reaches 59.4%, and the stability is good.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to the examples. The reagents used in the examples of the present invention are all commercially available.
Example 1
Silica sol (SiO 2 weight percentage content is 40%) is selected as a silicon source, sodium metaaluminate is selected as an aluminum source, tetrabutylammonium hydroxide is adopted as a template agent, hexadecyltrimethylammonium bromide is adopted as a structure directing agent, alkali metal hydroxide is selected from sodium hydroxide, Cu salt is selected from copper nitrate, Zn salt is selected from zinc nitrate, the tetrabutylammonium hydroxide is weighed according to the molar ratio of 0.01Cu:0.05Zn:25SiO2:0.5Al2O3:0.2 organic ammonium template agent: 0.05 structure directing agent: 5NaOH:2000 deionized water, crystallization is carried out for 48 hours at 160 ℃, after washing and drying, 1mol/L NH4NO3 solution is used for processing for 6 hours at 65 ℃, washing is carried out, drying is carried out for 24 hours at 100 ℃, finally, the catalyst is placed into a muffle furnace, roasting is carried out for 5 hours at 500 ℃, and extrusion molding is carried out to obtain the catalyst C-1.
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 150 ℃, then feeding the preheated methanol into a reaction tube at 380 ℃, controlling the feeding flow at 0.2ml/min, the reaction pressure at 1.0MPa, and the N content2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 2
Selecting ethyl orthosilicate as a silicon source, selecting sodium metaaluminate as an aluminum source, adopting tetraethyl ammonium hydroxide as a template agent, adopting hexadecyl trimethyl ammonium bromide as a structure directing agent, selecting potassium hydroxide as an alkali metal hydroxide, selecting copper nitrate as a Cu salt, selecting zinc nitrate as a Zn salt, weighing according to the molar ratio of 0.05Cu:0.1Zn:30SiO2:0.5Al2O3:0.3 organic ammonium template agent: 0.07 structure directing agent: 7KOH:2700 deionized water, fully mixing, crystallizing at 180 ℃ for 48 hours, washing and drying, treating with 1mol/L NH4NO3 solution at 65 ℃ for 6 hours, washing, drying at 120 ℃ for 48 hours, finally placing in a muffle furnace, roasting at 550 ℃ for 4 hours, extruding and molding to obtain the catalyst C-2.
Catalyst C-2 was crushed into 20-40 mesh particles, and 3ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, and the results are shown in Table 1.
Example 3
Silica sol (SiO 2 weight percentage content is 40%) is selected as a silicon source, aluminum isopropoxide is selected as an aluminum source, tetrapropylammonium hydroxide is adopted as a template agent, polyethylene glycol is adopted as a structure directing agent, alkali metal hydroxide is selected from sodium hydroxide, Cu salt is selected from copper nitrate, Zn salt is selected from zinc nitrate, the aluminum oxide is weighed according to the molar ratio of 0.1Cu:0.2Zn:50SiO2:0.5Al2O3:0.4 organic ammonium template agent: 0.1 structure directing agent: 10NaOH:4000 deionized water, after full mixing, crystallization is carried out for 24 hours at 200 ℃, after washing and drying, 1mol/L NH4NO3 solution is used for processing for 6 hours at 65 ℃, washing is carried out, drying is carried out for 36 hours at 110 ℃, finally, the mixture is put into a muffle furnace, roasting is carried out for 4 hours at 600 ℃, and strip extrusion molding is carried out to obtain the catalyst C-3.
Catalyst C-3 was crushed into 20-40 mesh particles, and 3ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, and the results are shown in Table 1.
Example 4
Silica sol (SiO 2 weight percentage content is 40%) is selected as a silicon source, aluminum isopropoxide is selected as an aluminum source, tetrabutylammonium bromide is adopted as a template agent, polyhexadecyltrimethylammonium bromide is adopted as a structure directing agent, potassium hydroxide is selected as an alkali metal hydroxide, copper nitrate is selected as a Cu salt, zinc nitrate is selected as a Zn salt, the components are weighed according to the molar ratio of 0.01Cu:0.2Zn:40SiO2:0.5Al2O3:0.25 organic ammonium template agent: 0.08 structure directing agent: 8KOH:3000 deionized water, fully mixed, crystallized at 160 ℃ for 96 hours, washed and dried, treated with 1mol/L NH4NO3 solution at 65 ℃ for 6 hours, washed, dried at 110 ℃ for 36 hours, finally placed into a muffle furnace, roasted at 500 ℃ for 6 hours, extruded and molded to obtain the catalyst C-4.
Catalyst C-4 was crushed into 20-40 mesh particles, and 3ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, and the results are shown in Table 1.
Example 5
Selecting tetraethoxysilane as a silicon source, selecting aluminum isopropoxide as an aluminum source, selecting tetrabutylammonium hydroxide as a template agent, selecting polyethylene glycol as a structure directing agent, selecting potassium hydroxide as an alkali metal hydroxide, selecting copper nitrate as a Cu salt, selecting zinc nitrate as a Zn salt, weighing according to the molar ratio of 0.01Cu:0.2Zn:40SiO2:0.5Al2O3:0.25 organic ammonium template agent: 0.08 structure directing agent: 8KOH:3000 deionized water, fully mixing, crystallizing at 160 ℃ for 96 hours, washing and drying, treating with 1mol/L NH4NO3 solution at 65 ℃ for 6 hours, washing, drying at 110 ℃ for 36 hours, finally placing in a muffle furnace, roasting at 500 ℃ for 6 hours, and extruding and molding to obtain the catalyst C-5.
Catalyst C-5 was crushed into 20-40 mesh particles, and 3ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, and the results are shown in Table 1.
Example 6
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 130 ℃, then feeding the preheated methanol into a reaction tube at 350 ℃, and controlling the feeding flow at 0.1ml/min, the reaction pressure at 0.2MPa and the N content2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 7
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 180 ℃, then feeding the preheated methanol into a reaction tube at 400 ℃, controlling the feeding flow at 0.3ml/min, the reaction pressure at 1.5MPa, and the N content2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 8
Crushing the catalyst C-1 into particles of 20 meshes to 40 meshes,3ml of catalyst is loaded in a fixed bed reactor, methanol mixed with 5 percent (Vol percent) of water is preheated in a preheater at 180 ℃, then enters a reaction tube at 450 ℃, the feeding flow is controlled at 0.2ml/min, the reaction pressure is 1.0MPa, and N is added2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 9
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 180 ℃, then feeding the preheated methanol into a reaction tube at 400 ℃, controlling the feeding flow at 0.3ml/min, the reaction pressure at 1.5MPa, and the N content2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 10
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 130 ℃, then feeding the preheated methanol into a reaction tube at 400 ℃, and controlling the feeding flow at 0.15ml/min, the reaction pressure at 0.5MPa and the N content2The flow rate was 6 ml/min. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 11
Crushing the catalyst C-1 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 150 ℃, then feeding the preheated methanol into a reaction tube at 380 ℃, controlling the feeding flow at 0.2ml/min, the reaction pressure at 1.0MPa, and the N content2The flow rate was 6 ml/min. The product after the reaction was condensed, and the liquid phase after the reaction for 200 hours was sampled and analyzed, and the reaction results are shown in Table 1.
Comparative example 1
The preparation method of the catalyst for preparing the aromatic hydrocarbon by using the methanol disclosed in the patent CN109701598A is adopted to prepare the catalyst C-6, the catalyst C-6 is crushed into particles of 20 meshes to 40 meshes, 3ml of the catalyst is loaded in a fixed bed reactor, the methanol mixed with 5 percent (Vol percent) of water enters a 380 ℃ reaction tube after being preheated in a preheater at 150 ℃, the feeding flow is controlled at 0.2ml/min, the reaction pressure is 1.0MPa, and N is2The flow rate was 6 ml/min. Condensing the reaction product, sampling and analyzing the liquid phase,the reaction results are shown in Table 1.
Comparative example 2
Crushing the catalyst C-6 into particles of 20-40 meshes, loading 3ml of catalyst into a fixed bed reactor, preheating methanol mixed with 5% (Vol%) water in a preheater at 150 ℃, then feeding the preheated methanol into a reaction tube at 380 ℃, controlling the feeding flow at 0.2ml/min, the reaction pressure at 1.0MPa, and the N content2The flow rate was 6 ml/min. The product after the reaction was condensed, and the liquid phase after the reaction for 200 hours was sampled and analyzed, and the reaction results are shown in Table 1.
TABLE 1 reaction results for methanol to aromatics
| Examples | Yield of aromatic hydrocarbons,% | BTX yield,% |
| Example 1 | 71.2 | 64.3 |
| Example 2 | 69.8 | 63.2 |
| Example 3 | 67.9 | 60.4 |
| Example 4 | 67.8 | 55.7 |
| Example 5 | 68.4 | 56.7 |
| Example 6 | 72.4 | 65.3 |
| Example 7 | 66.4 | 51.2 |
| Example 8 | 67.5 | 58.2 |
| Example 9 | 65.4 | 50.7 |
| Example 10 | 69.1 | 57.9 |
| Example 11 | 69.8 | 59.4 |
| Comparative example 1 | 56.7 | 43.5 |
| Comparative example 2 | 46.4 | 35.2 |
As can be seen from the data in Table 1, the yield of the aromatic hydrocarbon of the catalyst for preparing aromatic hydrocarbon from methanol prepared by the method of the invention reaches 71.2% in the initial reaction stage, and the yield of BTX reaches 64.3%; after 200h, the yield of the aromatic hydrocarbon still reaches 69.8 percent, and the yield of BTX reaches 59.4 percent. The catalyst prepared by the preparation method of the catalyst for preparing aromatic hydrocarbon from methanol disclosed in patent CN109701598A has the advantages that the yield of aromatic hydrocarbon reaches 56.7%, the yield of BTX reaches 43.5%, but the activity of the catalyst is obviously reduced after 200 hours, the yield of aromatic hydrocarbon is reduced to 46.4%, and the yield of BTX is reduced to 35.2%.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The catalyst for preparing the aromatic hydrocarbon from the methanol is characterized by comprising active components of Cu, Zn, Al and Si; the molar ratio of Cu to Zn to Al to Si = 0.01-0.1: 0.05-0.2: 1: 25-50; the Cu is derived from copper salt, the Zn is derived from zinc salt, the Al is derived from sodium metaaluminate or aluminum isopropoxide, and the Si is derived from silica sol or ethyl orthosilicate.
2. The method for preparing the catalyst according to claim 1, wherein the catalyst is prepared by a sol-gel method, comprising the steps of:
(1) dissolving copper salt, zinc salt, organic ammonium template agent, structure directing agent, aluminum source and alkali metal hydroxide in deionized water, preparing a solution after all the components are dissolved, adding a silicon source into the solution under the stirring state, and continuously stirring for 0.5-2h to obtain raw material mixture gel;
(2) controlling the temperature of the gel obtained in the step (1) at 160-200 ℃ for 24-96 h, and converting the gel into powder after temperature control treatment;
(3) washing the powder obtained in the step (2), filtering, drying, and adding NH4NO3Stirring the solution and carrying out hydrothermal treatment;
(4) and washing and drying the finally obtained solid, roasting, extruding and forming to obtain the catalyst.
3. The method according to claim 2, wherein the copper salt, the zinc salt, and the nitrate salts thereof in step (1); the organic ammonium template is selected from tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide or tetrabutyl ammonium bromide; the structure directing agent is selected from cetyl trimethyl ammonium bromide or polyethylene glycol; the alkali metal hydroxide is selected from sodium hydroxide or potassium hydroxide.
4. The method according to claim 2, wherein the raw material mixture in the step (1) contains Cu, Zn, and SiO in a molar ratio2:Al2O3The organic ammonium template is a structure directing agent, and the ratio of alkali metal oxide to deionized water is 0.01-0.1: 0.05-0.2: 25-50: 0.5: 0.2-0.4: 0.05-0.1: 5-10: 2000-4000.
5. The preparation method according to claim 2, wherein the gel in the step (2) is filled into a reaction kettle and placed into an oven for temperature control treatment.
6. The method of claim 5, wherein the reaction vessel is a polytetrafluoroethylene-lined reaction vessel.
7. The method according to claim 2, wherein in the step (3), the powder obtained in the step (2) is washed, filtered, dried, and added with 1mol/lNH4NO3The solution was hydrothermally treated for 6 hours at 65 ℃ with stirring.
8. The preparation method according to claim 2, wherein in the step (4), the drying temperature is 100-120 ℃, the drying time is 24-48 hours, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours.
9. The application of the catalyst according to claim 1, wherein the catalyst is used for a reaction for preparing aromatic hydrocarbon from methanol, and the reaction conditions are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 0.2-1.5 MPa, and the methanol feeding flow is 0.1-0.3 ml/min.
10. The application of the catalyst as claimed in claim 7, wherein the catalyst is loaded into a fixed bed reactor when the catalyst is used for preparing aromatic hydrocarbon from methanol, and the methanol is preheated before the reaction, wherein the preheating temperature is 130-180 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537315A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst for preparation of aromatic hydrocarbons from methanol and preparation method thereof |
| CN103950951A (en) * | 2014-04-25 | 2014-07-30 | 清华大学 | Method for synthesizing heteroatomic ZSM-5 molecular sieve and application thereof |
| CN106391104A (en) * | 2016-07-05 | 2017-02-15 | 天津工业大学 | Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration |
| CN106582797A (en) * | 2016-11-25 | 2017-04-26 | 厦门大学 | Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum |
| CN108435246A (en) * | 2018-02-01 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of multi-stage porous same order elements Ga-ZSM-5 molecular sieve catalysts |
| CN109908949A (en) * | 2019-03-25 | 2019-06-21 | 北京化工大学 | A kind of bimetallic-modified nano-HZSM-5 zeolite catalyst, preparation method and the usage |
| CN109967118A (en) * | 2019-05-05 | 2019-07-05 | 北京化工大学 | A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene |
-
2019
- 2019-10-15 CN CN201910977049.5A patent/CN112657498A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537315A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst for preparation of aromatic hydrocarbons from methanol and preparation method thereof |
| CN103950951A (en) * | 2014-04-25 | 2014-07-30 | 清华大学 | Method for synthesizing heteroatomic ZSM-5 molecular sieve and application thereof |
| CN106391104A (en) * | 2016-07-05 | 2017-02-15 | 天津工业大学 | Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration |
| CN106582797A (en) * | 2016-11-25 | 2017-04-26 | 厦门大学 | Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum |
| CN108435246A (en) * | 2018-02-01 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of multi-stage porous same order elements Ga-ZSM-5 molecular sieve catalysts |
| CN109908949A (en) * | 2019-03-25 | 2019-06-21 | 北京化工大学 | A kind of bimetallic-modified nano-HZSM-5 zeolite catalyst, preparation method and the usage |
| CN109967118A (en) * | 2019-05-05 | 2019-07-05 | 北京化工大学 | A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene |
Non-Patent Citations (1)
| Title |
|---|
| 汪哲明等: "甲醇制芳烃催化剂研究进展", 《化工进展》 * |
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