CN113499795B - Hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst, and preparation method and application thereof - Google Patents
Hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst, and preparation method and application thereof Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 2-methylimidazole hydrochloride modified hydrogen Chemical class 0.000 title claims abstract description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 72
- YZPNFYQRPJKWFJ-UHFFFAOYSA-N 2-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CC1=NC=CN1 YZPNFYQRPJKWFJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 20
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 18
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- 230000006315 carbonylation Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract 1
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- 239000002253 acid Substances 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 240000008114 Panicum miliaceum Species 0.000 description 2
- 235000007199 Panicum miliaceum Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- CVCFHGVTPLNQRD-UHFFFAOYSA-N 1,3-dimethyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CN1C[NH+](C)C=C1 CVCFHGVTPLNQRD-UHFFFAOYSA-N 0.000 description 1
- ODJKHOBNYXJHRG-UHFFFAOYSA-N 1,3-dimethylimidazole Chemical compound CN1[CH]N(C)C=C1 ODJKHOBNYXJHRG-UHFFFAOYSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000370001 Hantavirus Liu Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst, a preparation method and application thereof, and belongs to the technical field of molecular sieve catalysts. The preparation method comprises the following steps: mixing hydrochloric acid and 2-methylimidazole hydrochloride solution, adding powdery hydrogen-type mordenite, uniformly stirring, carrying out ion exchange at a certain temperature, and then filtering, washing and drying to obtain the modified hydrogen-type mordenite catalyst. The catalyst has the advantages of simple preparation process, low cost, no use of expensive noble metals, and good carbonylation activity, selectivity and stability, and is used for catalyzing the carbonylation of dimethyl ether (DME) to prepare Methyl Acetate (MA).
Description
Technical Field
The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a hydrogen-type mordenite catalyst modified by hydrochloric acid and 2-methylimidazolium hydrochloride, and a preparation method and application thereof.
Background
The ethanol is used as the ethanol gasoline additive for vehicles, has excellent explosion-proof and earthquake-proof performance, and the tail gas does not contain SO x 、NO x And little CO emission, and the like, ethanol gasoline is advocated to be used by many countries. Ethanol is also a basic raw material of many chemicals and foods, such as intermediates of chemical products, synthetic detergents, paints, etc., and is medically used for disinfection, so that the demand is enormous.
The ethanol production method comprises an ethylene hydration method, a biomass fermentation method, ethanol preparation by synthetic gas and the like. The conversion rate of the ethylene hydration method is very low, and the production energy consumption is high. The biomass fermentation method comprises hydrolysis fermentation of sucrose, starch and cellulose, and the like, and the main raw materials for producing fuel ethanol in China are grain crops such as corn, cassava and the like, wherein the corn alcohol yield ratio reaches 79%. However, the production of fuel ethanol by using crops (including sucrose) such as grains as raw materials is bound to cause the situation that the production of fuel ethanol strives for grains with people and grains with livestock, and the contradiction between the low ethanol productivity and the huge demand cannot be solved. The route of preparing MA (methyl acetate) from synthesis gas through carbonylation of DME (dimethyl ether) and then preparing ethanol through hydrogenation has mild reaction conditions (1.5MPa,220 ℃), cheap and easily-obtained raw materials, high atom economic efficiency, environmental protection and capability of simultaneously solving the problems of excess DME (and methanol) productivity and insufficient ethanol and MA productivity. In this route, DME is carbonylated with CO to produce MA, which is hydrogenated over a copper-based catalyst to produce ethanol. Among them, the hydrogenation of MA to ethanol is industrially very mature, and the key technology lies in the research and development of the carbonylation reaction of DME and CO and the catalyst thereof.
Carbonylation catalysts currently under investigation are: noble metal-iodide composite catalysts, heteropolyacid catalysts, molecular sieve catalysts and the like. The noble metal-iodide catalyst is a homogeneous reaction system, the catalyst and the product are not easy to separate, the noble metal is expensive, and simultaneously, the catalyst contains I - The solution is highly corrosive to the equipment. The heteropoly acid catalyst still needs to use precious metals such as Rh to obtain higher MA yield, and the selectivity and the stability of the heteropoly acid catalyst are also required to be improved. The molecular sieve catalyst has regular and uniform pore channels, large specific surface area, easily-adjusted acidity, good thermal stability and low price. The commonly used molecular sieves are HMOR, FER, SSZ-13, ZSM-5, HSUZ-4, BEA, USY and EMT, wherein the HMOR (hydrogen mordenite) catalyst has higher MA yield and selectivity and is an ideal catalyst for the DME carbonylation reaction. However, HMOR is rapidly deactivated during the carbonylation reaction by carbon deposition from its twelve-membered ring (12-MR). In order to improve the activity and stability of HMOR, technicians modify the HMOR by using transition metals such as Cr, Co, Cu and Zn and noble metals such as Ag and Pt, selectively dealuminate the HMOR by 12-MR, synthesize the ultra-small nano HMOR and the like, and the activity is greatly improved, but the improvement effect on the stability of the catalyst is little. Adopts pyridine pre-adsorption method, in-situ carbonization method and fatty amine acidThe salt solution selective ion exchange method and the like modify the HMOR, so that the stability of the HMOR is improved to a certain extent. Shenwite et al (patent No. CN101613274B) use NaOH, KOH or other alkali or hydrochloric acid, nitric acid or other to pretreat HMOR, then use pyridine organic amine to carry out pre-adsorption, the alkaline pyridine molecule selectively enters 12-MR to react with Bronsted acid (B acid), and the eight-membered ring (8-MR) acid site is preserved, the service life of the catalyst is prolonged, but because of the problems of pyridine in-situ carbonization at high temperature and shielding of B acid at the junction of 12-MR and 8-MR, DME conversion rate is reduced (DME conversion rate is reduced)<30%). Liuhong super et al (patent number: CN106890671B) adopts pyridine compound to purge EMT zeolite after acid treatment, and the service life of catalyst is obviously prolonged>3000h) However, most of the modified sample DME conversion rate is lower than 30%, and the catalyst preparation process is complicated. King gold rod, etc. (patent numbers: CN107537549A, CN107537548A) adopt HMOR to pre-adsorb unsaturated hydrocarbon and nitrogen-containing heterocyclic compound, and then carry out high-temperature in-situ carbonization reaction to obtain the modified molecular sieve, wherein the DME conversion rate is higher, but the service life of the catalyst is only 24-47 h. Liu Yahua et al (patent No.: CN108160100A) use pyridine to react with the B acid site of HMOR12-MR, and then use Cu (NO) 3 ) 2 、Zn(NO 3 ) 2 When the metal salt is used for modifying the 8-MR, the stability of the catalyst is obviously improved, but the conversion rate of sample DME is lower than 50%. Fatty amine and B acid proton of HMOR12-MR are adopted for selective ion exchange in Liuzhong people, Zhuwenliang and the like (DOI: 10.1039/d0cy00125B) to cover 12-MR carbon deposition reaction active centers, the carbon deposition problem is perfectly solved, the conversion rate of a catalyst DME reaches 50%, the MA selectivity approaches 100%, the service life reaches more than 210h, but because the selected fatty amine is too large in volume, the specific surface area of a modified molecular sieve is only 1/10, and the activity of the catalyst is influenced to a certain extent. Liushi Heng et al (DOI: 10.1016/j. cat com.2020.106161) adopts alkyl imidazolium ions such as 1, 3-dimethyl imidazole, 1-butyl-3 methyl imidazole and the like to modify HMOR, the DME conversion rate is close to 70%, the MA selectivity reaches 100%, and certain stability is shown, but because the boiling point of the used imidazole compounds is low, the slow desorption of nitrogen heterocyclic molecules leads the catalyst to be gradually deactivated. In addition, 1, 3-dimethylimidazole hydrochloride which is nearly neutralThe solution also shielded the acid site of B contributing to the carbonylation in 12-MR, which had a certain effect on the activity, with a maximum MA space time yield of 3.22 mmol/(g.h). The Panicum miliaceum et al (CN 109939669A) adopts organic base to modify MOR and is applied to preparing low-carbon olefin by carbon monoxide hydrogenation, but the traditional organic base modification method can not realize the purpose of selectively shielding B acid in MOR12-MR, and the expected effect is difficult to obtain when the Panicum miliaceum et al (CN 109939669A) is used for DME carbonylation reaction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a hydrochloric acid and 2-methylimidazolium hydrochloride modified hydrogen-type mordenite catalyst, and a preparation method and application thereof, so as to solve the problems of serious carbon deposition, low activity, short service life, high cost and the like of the existing HMOR catalyst. The invention adopts hydrochloric acid and 2-methylimidazole hydrochloride solution to carry out ion exchange on HMOR, wherein the size of corresponding cations of 2-methylimidazole is far smaller than that of a 12-MR pore passage
And the 8-MR bore
The size of the acid B is similar, the acid B can enter 12-MR to perform ion exchange with the acid B in the pore canal, but the acid B is difficult to enter 8-MR, and the acid B at the junction of the 12-MR and the 8-MR and the acid B in the 8-MR are reserved. In addition, the environment of the acid solution is cleaned of non-framework aluminum, the boiling point of 2-methylimidazole is as high as 268 ℃, and the 2-methylimidazole is difficult to desorb after entering the HMOR pore channel, so that the B acid in the pore channel is difficult to regenerate. Therefore, the activity and the service life of the HMOR carbonylation reaction of the catalyst are obviously improved, and the highest MA space-time yield reaches 4.78 mmol/(g.h) while the carbonylation reaction is kept stable. In addition, the catalyst of the invention has simple preparation process, does not use noble metals or expensive raw materials, and has low price.
The purpose of the invention is realized by at least one of the following technical solutions.
A preparation method of a hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst comprises the following steps:
1) dissolving 2-methylimidazole hydrochloride in water, adding concentrated hydrochloric acid, diluting with water, and preparing a mixed solution;
2) adding powdery hydrogen mordenite into the mixed solution, uniformly stirring, carrying out ion exchange at a certain temperature, and then filtering, washing and drying to obtain the modified hydrogen mordenite catalyst.
Preferably, the molar ratio of the 2-methylimidazole hydrochloride to the HCl in the mixed solution in the step 1) is 1-1000.
Preferably, the molar ratio of the 2-methylimidazole hydrochloride to the HCl in the mixed solution in the step 1) is 1-3.2.
Preferably, the concentration of the 2-methylimidazole hydrochloride in the mixed solution in the step 1) is 0.2-1.6 mol/L.
Preferably, the concentration of the 2-methylimidazole hydrochloride in the mixed solution in the step 1) is 1-1.6 mol/L.
Preferably, the ion exchange temperature in step 2) is 40-100 ℃.
Preferably, the ion exchange temperature in step 2) is 40-80 ℃.
Preferably, the molar ratio of the 2-methylimidazole hydrochloride to the HCl in the mixed solution is 1; the concentration of the 2-methylimidazole hydrochloride in the mixed solution is 1.6 mol/L; the ion exchange temperature is 80 ℃; the ion exchange time was 60 min.
The hydrogen mordenite catalyst modified by hydrochloric acid and 2-methylimidazole hydrochloride prepared by the preparation method.
The application of the hydrochloric acid and 2-methylimidazolium hydrochloride modified hydrogen mordenite catalyst in the preparation of methyl acetate by carbonylation of dimethyl ether is characterized in that dimethyl ether and CO are used as reaction gases, and the molar ratio of the dimethyl ether to the CO is 1: 10-50; ar or N 2 As the diluent gas, the volume fraction of the diluent gas is 0-50%; the reaction temperature is 200-250 ℃, the reaction pressure is 1-5 MPa, and the reaction space velocity is 2000-20000 mL-g -1 ·h -1 。
Compared with the prior art, the invention has the following advantages:
the catalyst of the invention can be used for preparing MA by DME carbonylation reaction, and has the advantages of good carbonylation activity, selectivity and stability, simple preparation process, low price of raw materials and no use of noble metals.
Drawings
FIG. 1 is a plot of DME conversion as a function of reaction time for varying molar ratios of hydrochloric acid to MeIm & HCl solution modified HMOR15, pure MeIm & HCl modified HMOR15, and unmodified HMOR 15; reaction conditions are as follows: 220 ℃, 1.5MPa, GHSV 4500mL g -1 ·h -1 ，DME/CO/N 2 ＝1/19/5。
FIG. 2 is a graph of MA selectivity as a function of reaction time for hydrochloric acid and MeIm & HCl solution modified HMOR15, pure MeIm & HCl modified HMOR15, and unmodified HMOR15 with 2-methylimidazole hydrochloride to HCl molar ratios of 1 and 1000, respectively; the reaction conditions are as follows: 220 ℃, 1.5MPa, GHSV 4500mL g -1 ·h -1 ，DME/CO/N 2 ＝1/19/5。
FIG. 3 is a plot of DME conversion as a function of reaction time for varying MeIm & HCl concentrations of hydrochloric acid and MeIm & HCl solution modified HMOR 15; reaction conditions are as follows: 220 ℃, 1.5MPa, GHSV 4500mL g -1 ·h -1 ，DME/CO/N 2 ＝1/19/5。
FIG. 4 is a graph of MA selectivity versus reaction time for hydrochloric acid of different MeIm & HCl concentrations and MeIm & HCl solution modified HMOR 15; reaction conditions are as follows: 220 ℃, 1.5MPa, GHSV 4500mL g -1 ·h -1 ，DME/CO/N 2 ＝1/19/5。
FIG. 5 is a graph of DME conversion as a function of reaction time for varying ion exchange temperatures of hydrochloric acid and MeIm & HCl solution modified HMOR 15; reaction conditions are as follows: 220 ℃, 1.5MPa, GHSV 4500mL g -1 ·h -1 ，DME/CO/N 2 ＝1/19/5。
Brief description of the drawings:
HMOR 15: hydrogen mordenite with a silica to alumina ratio of 15;
TOS: reaction time;
GHSV: gas phase volumetric space velocity;
2-methylimidazolium hydrochloride: MeIm. HCl.
Detailed Description
The following examples and figures further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Comparative example 1
The HMOR (silicon to aluminum ratio of 15) was placed in a muffle furnace and calcined at 3K/min up to 500 ℃ for 3h, and the sample was identified as HMOR 15. 0.2g of 40-60 mesh HMOR15 was used for the DME carbonylation reaction and the results of the performance tests are shown in FIGS. 1 and 2.
Comparative example 2
1g of HMOR15 was added to 10mL of a 1mol/L solution of MeIm HCl (pH 6.4), ion exchanged for 1h in a water bath at 80 ℃ with stirring, filtered and the filter cake was washed 3 times with deionized water. The resulting sample was dried overnight in an oven at 60 ℃ and pelletized and scored as MeIm. HCl-HMOR 15. 0.2g of 40-60 mesh MeIm HCl-HMOR15 was used for DME carbonylation and the results of the performance tests are shown in FIGS. 1 and 2.
Example 1
1g of HMOR15 was added to 10mL of a mixed solution of hydrochloric acid and Meim & HCl having molar ratios of 2-methylimidazole hydrochloride to HCl of 1, 1.6, 3.2, 32 and 1000, respectively, and a Meim & HCl concentration of 1mol/L, ion-exchanged for 1h in a water bath at 80 ℃ with stirring, filtered and the filter cake was washed 3 times with deionized water. The resulting samples were dried overnight in an oven at 60 ℃ and pelletized by compression, with the samples being identified in order as HMOR15(1-1-80), HMOR15(1.6-1-80), HMOR15(3.2-1-80), HMOR15(32-1-80) and HMOR15 (1000-1-80). 0.2g of 40-60 mesh samples were weighed for DME carbonylation respectively, and the performance test results are shown in FIG. 1 and FIG. 2.
Example 2
1g of HMOR15 was added to 10mL of a mixed solution of 2-methylimidazole hydrochloride and HCl in a molar ratio of 3.2 and MeIm HCl concentrations of 0.2mol/L, 1mol/L and 1.6mol/L, respectively, and ion-exchanged for 1 hour in a water bath at 80 ℃ with stirring, filtered and the filter cake was washed 3 times with deionized water. And drying the obtained product in an oven at 60 ℃ overnight, tabletting and granulating, wherein the product is marked as HMOR15(3.2-0.2-80), HMOR15(3.2-1-80) and HMOR15(3.2-1.6-80) in sequence. 0.2g of 40-60 mesh samples were weighed out separately for DME carbonylation reactions, and the results of the performance tests are shown in FIGS. 3 and 4.
Example 3
1g of HMOR15 was added to 10mL of a mixed solution of 2-methylimidazole hydrochloride and HCl in a molar ratio of 3.2 and a MeIm & HCl concentration of 1mol/L, ion exchanged for 1h in a 40 ℃ water bath with stirring, filtered and the filter cake was washed 3 times with deionized water. The sample was dried overnight in an oven at 60 ℃ and pelletized and identified as HMOR15 (3.2-1-40). The above procedure was repeated except that the ion exchange temperature was changed to 80 ℃ and 100 ℃ respectively, and the resulting samples were designated as HMOR15(3.2-1-80) and HMOR15(3.2-1-100), respectively. 0.2g of 40-60 mesh samples were weighed out separately for the DME carbonylation reaction and the results of the performance tests are shown in FIG. 5.
Claims (3)
1. The application of the hydrochloric acid and 2-methylimidazolium hydrochloride modified hydrogen mordenite catalyst in preparation of methyl acetate by carbonylation of dimethyl ether is characterized in that dimethyl ether and CO are used as reaction gases, and the molar ratio of the dimethyl ether to the CO is 1: 10-50; ar or N 2 As the diluent gas, the volume fraction of the diluent gas is 0-50%; the reaction temperature is 200-250 ℃, the reaction pressure is 1-5 MPa, and the reaction space velocity is 2000-20000 mL-g -1 ·h -1 ；
The preparation method of the hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst comprises the following steps:
1) dissolving 2-methylimidazolium hydrochloride in water, adding concentrated hydrochloric acid, diluting with water, and preparing to obtain a mixed solution; the molar ratio of the 2-methylimidazole hydrochloride to the HCl in the mixed solution is 1-3.2; the concentration of the 2-methylimidazole hydrochloride in the mixed solution is 1-1.6 mol/L;
2) and adding powdery hydrogen mordenite into the mixed solution, uniformly stirring, carrying out ion exchange, filtering, washing and drying to obtain the hydrochloric acid and 2-methylimidazolium hydrochloride modified hydrogen mordenite catalyst.
2. Use according to claim 1, wherein the ion exchange temperature in step 2) is 40-80 ℃.
3. The use according to claim 2, wherein the molar ratio of 2-methylimidazole hydrochloride to HCl in the mixed solution is 1; the concentration of the 2-methylimidazole hydrochloride in the mixed solution is 1.6 mol/L; the dosage of the powdery hydrogen mordenite and the mixed solution is 1g/10 mL; the temperature of the ion exchange is 80 ℃; the ion exchange time was 60 min.
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