CN113244952A - Modification method for simultaneously improving activity and service life of HMOR molecular sieve catalyst for carbonylation of dimethyl ether - Google Patents
Modification method for simultaneously improving activity and service life of HMOR molecular sieve catalyst for carbonylation of dimethyl ether Download PDFInfo
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- molecular sieve
- hmor
- nitrogen
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- heterocyclic compound
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 124
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 35
- 230000006315 carbonylation Effects 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 13
- 238000002715 modification method Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 31
- 239000004202 carbamide Substances 0.000 claims description 31
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims description 28
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 abstract description 7
- 239000010457 zeolite Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 15
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- 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
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- 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
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0249—Ureas (R2N-C(=O)-NR2)
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- B01J35/643—
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- B01J35/67—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
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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
- B01J2229/38—Base treatment
Abstract
The invention discloses a modification method for simultaneously improving the activity and the service life of an HMOR molecular sieve catalyst for dimethyl ether carbonylation, which comprises the following steps: putting the dried HMOR molecular sieve into a double-component mixed alkali solution, and stirring for 0.1-2 hours at the temperature of 25-95 ℃; or introducing nitrogen into the two-component mixed alkali solution, and drying the HMOR molecular sieveIntroducing N at 25-100 deg.C2Absorbing steam in the double-component mixed alkali solution until the absorption is saturated; and (3) placing the HMOR molecular sieve with saturated adsorption in an inert atmosphere for heat treatment to obtain the modified HMOR molecular sieve catalyst capable of regulating and controlling the pore structure and the acid distribution. The invention simultaneously prepares the meso-microporous HMOR molecular sieve and selectively shields acid sites of the HMOR molecular sieve which are easy to generate side reaction, retains active sites with carbonylation function, improves reaction mass transfer efficiency, and obviously improves the catalytic efficiency of the HMOR zeolite molecular sieve for catalyzing the carbonylation of dimethyl ether and the service life of the catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst modification, in particular to a modification method for simultaneously improving the activity and service life of a HMOR molecular sieve catalyst for dimethyl ether carbonylation.
Background
Methyl acetate is an important chemical product and a good environment-friendly organic solvent, and can replace acetone, butanone, cyclopentane and the like to be applied to the production of resin, leather and the like. The downstream products of the method, such as acetic acid, acetic anhydride, methyl acrylate, ethanol and the like, are important chemical raw materials. The ethanol, as a novel fuel and gasoline additive, has the advantages of cleanness and high efficiency. At present, the industrial ethanol generation method mainly comprises the steps of taking petroleum resources as raw materials, carrying out chemical synthesis, taking grain biomass as raw materials, and preparing the raw materials by a biological fermentation method. Due to the shortage of petroleum resources and the invaluability of food resources, the development of a path for preparing ethanol from coal resources has higher economic significance. The technical path of preparing the methyl acetate by the carbonylation of the dimethyl ether and preparing the ethanol by further hydrogenating the methyl acetate opens up an efficient path from non-petroleum-based carbon-containing resources to the preparation of clean energy ethanol. Therefore, the research on the problem of preparing the methyl acetate by the carbonylation of the dimethyl ether has important significance.
The prior dimethyl ether carbonylation preparation of methyl acetate mainly adopts homogeneous phase and heterogeneous phase catalytic systems. Homogeneous catalysts are difficult to separate from the product, increase separation costs, and use noble metals and halide promoters, which are more corrosive to equipment (J Chem Soc, Chem Comm 1994, (8), 947-. Currently, molecular sieves are considered to be the most economical and environmentally friendly catalysts for the carbonylation of dimethyl ether (angelw.chem, int.ed., 2006, (10), 1617-. Among them, Hydrogen Mordenite (HMOR) has been widely studied due to its high catalytic activity and methyl acetate selectivity. However, carbon deposits are readily produced in the twelve-membered ring of the MOR molecular sieve during the carbonylation process, resulting in rapid deactivation of the catalyst. At present, post-treatment modification is considered to be a simple and effective means of increasing the lifetime of the MOR catalyst. Although the conventional metal modification and alkali treatment modification can improve the catalyst life, the catalyst is deactivated with an increase in the reaction time (20 hours or more). In addition, another main factor limiting the dimethyl ether carbonylation reaction is low dimethyl ether conversion efficiency, and methods for improving the dimethyl ether carbonylation mostly adopt expensive organic templates or complex modification methods of metal modification. So far, no method for simultaneously and obviously improving the activity and the stability of the dimethyl ether carbonylation catalyst exists. Therefore, the method has important significance for simultaneously improving the dimethyl ether conversion efficiency and the stability of the catalyst by utilizing a mild modification method.
Disclosure of Invention
The invention aims to provide a modification method for simultaneously improving the activity and the service life of a HMOR molecular sieve catalyst for dimethyl ether carbonylation, which can simultaneously obtain a meso-micro hierarchical pore structure and effectively shield an acid site in HMOR, so that the dimethyl ether carbonylation conversion efficiency and the service life of the catalyst are obviously improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a modification method for simultaneously improving the activity and the service life of a HMOR molecular sieve catalyst for carbonylation of dimethyl ether comprises the following steps:
(1) drying the HMOR molecular sieve in vacuum at the temperature of 100-300 ℃ to obtain the dried HMOR molecular sieve;
(2) putting the HMOR molecular sieve dried in the step (1) into a mixed solution of quaternary ammonium hydroxide and nitrogen-containing heterocyclic compound bi-component organic mixed base, and stirring for 0.1-2 hours at 25-50 ℃, wherein the mass ratio of the quaternary ammonium hydroxide to the nitrogen-containing heterocyclic compound is 1: 0.2;
or putting the HMOR molecular sieve dried in the step (1) into a mixed solution of urea and a nitrogen-containing heterocyclic compound bi-component organic mixed alkali, and stirring for 0.1-2 hours at 40-95 ℃, wherein the mass ratio of the urea to the nitrogen-containing heterocyclic compound is 1: 0.2;
or introducing nitrogen into a mixed solution of quaternary ammonium base and nitrogen-containing heterocyclic compound bi-component organic mixed base, placing the dried HMOR molecular sieve obtained in the step (1) in a container, heating to 25-100 ℃, introducing N2Adsorbed quaternary ammonium hydroxide and nitrogen-containing heterocyclic compound two-component organic mixed base steam, wherein the mass ratio of the quaternary ammonium hydroxide to the nitrogen-containing heterocyclic compound is 1: 0.2;
or introducing nitrogen into a mixed solution of urea and a nitrogen-containing heterocyclic compound bi-component organic mixed base, placing the dried HMOR molecular sieve obtained in the step (1) in a container, heating to 40-90 ℃, introducing N2The method comprises the following steps of (1) adsorbing two-component organic mixed alkali steam of urea and a nitrogen-containing heterocyclic compound, wherein the mass ratio of the urea to the nitrogen-containing heterocyclic compound is 1: 0.2;
(3) and (3) placing the HMOR molecular sieve adsorbing the two-component alkali solution in an inert atmosphere, and carrying out heat treatment at the temperature of 100 ℃ and 400 ℃ for 2 hours to obtain the HMOR molecular sieve catalyst modified by the two-component alkali substance.
Preferably, in the step (2), the mass ratio of the HMOR molecular sieve to the two-component organic mixed base of the quaternary ammonium base and the nitrogen-containing heterocyclic compound is 0.5-5: 1.
preferably, in the step (2), the mass ratio of the HMOR molecular sieve to the two-component organic mixed alkali of urea and the nitrogen-containing heterocyclic compound is 0.5-5: 1.
preferably, in step (2), the quaternary ammonium hydroxide is tetrapropylammonium hydroxide or tetraethylammonium hydroxide.
Preferably, in the step (2), the nitrogen-containing heterocyclic compound is any one or more of lutidine, diaminopyridine and piperidine.
Compared with the prior art, the method can simultaneously prepare the hierarchical pore molecular sieve and directionally regulate and control the acid distribution of HMOR molecular pore channels, can selectively shield acid sites which are easy to generate carbon deposition in twelve-membered rings of the HMOR molecular sieve while introducing mesopores, and reserves active sites with carbonylation functions in eight-membered rings. The catalyst has the double functions of improving the mass transfer rate of the dimethyl ether carbonylation reaction and shielding the active site generating the side reaction, and can obviously improve the conversion rate and the catalytic life of dimethyl ether carbonylation catalyzed by HMOR.
Drawings
FIG. 1 is an XRD pattern of HMOR molecular sieves prepared separately for examples 1, 3 and comparative example 7 of the present invention;
FIG. 2 is a graph showing N of HMOR molecular sieves prepared in examples 1 and 3 of the present invention and comparative example 7, respectively2An adsorption-desorption curve;
FIG. 3 is a plot of the pore size distribution of HMOR molecular sieves prepared separately for examples 1, 3 and comparative example 7 of the present invention;
FIG. 4 is a graph comparing the amount of acid in twelve membered rings of HMOR molecular sieves made separately in examples 1, 3 and comparative example 7 of the present invention;
fig. 5 is a graph of dimethyl ether carbonylation catalytic activity of modified HMOR molecular sieve prepared in example 1 of the present invention: (a) dimethyl ether conversion, (b) selectivity to product methyl acetate;
fig. 6 is a graph of dimethyl ether carbonylation catalytic activity of modified HMOR molecular sieve prepared in example 2 of the present invention: (a) dimethyl ether conversion, (b) selectivity to product methyl acetate;
fig. 7 is a graph of dimethyl ether carbonylation catalytic activity of HMOR molecular sieve prepared in comparative example 7: (a) dimethyl ether conversion, and (b) selectivity to product methyl acetate.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments, it should be noted that the raw material HMOR molecular sieve used in the following examples and comparative examples is not limited to the range of Si/Al ratio and the morphology structure.
Example 1
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
placing the obtained 20 g of molecular sieve sample into a closed reaction kettle, adding 20 g of mixed solution of tetrapropylammonium hydroxide and lutidine (the mass ratio of the tetrapropylammonium hydroxide to the lutidine is 1:0.2) into the reaction kettle, and stirring for 0.5 hour at 50 ℃;
putting the HMOR molecular sieve subjected to adsorption treatment on the mixture of tetrapropylammonium hydroxide and lutidine in N2And (3) carrying out heat treatment at 250 ℃ for 2 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Example 2
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
the 20 g molecular sieve sample obtained above was placed in a closed reaction vessel and heated to 50 ℃. 20 g of a mixed solution of tetrapropylammonium hydroxide and lutidine (mass ratio of tetrapropylammonium hydroxide to lutidine: 1:0.2) was charged into another solution tank, and N was added2Introducing into a solution tank of tetrapropylammonium hydroxide and lutidine, and adding N2The adsorbed tetrapropylammonium hydroxide and lutidine vapors were introduced into the reaction kettle for 30 minutes.
Placing the HMOR zeolite molecular sieve saturated in adsorption in N2And (3) carrying out heat treatment at 250 ℃ for 4 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Example 3
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
placing the obtained 20 g of molecular sieve sample into a closed reaction kettle, adding 20 g of mixed solution of urea and lutidine (the mass ratio of the urea to the lutidine is 1:0.2) into the reaction kettle, and stirring for 0.5 hour at 90 ℃;
putting HMOR treated by mixed alkali liquor of urea and lutidine into N2And (3) carrying out heat treatment at 250 ℃ for 2 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Example 4
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
the 20 g molecular sieve sample obtained above was placed in a closed reaction vessel and heated to 50 ℃. 20 g of mixed solution of urea and lutidine (the mass ratio of the urea to the lutidine is 1:0.2) is added into the other solution tank,will N2Introducing into a solution tank of urea and lutidine, and adding N2The adsorbed urea and lutidine vapors were passed into the reactor for 30 minutes.
Placing the HMOR zeolite molecular sieve saturated in adsorption in N2And (3) carrying out heat treatment at 250 ℃ for 4 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 1
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
placing the obtained 20 g of molecular sieve sample into a closed reaction kettle, adding 20 g of tetrapropyl ammonium hydroxide solution into the reaction kettle, and stirring for 0.5 hour at 50 ℃;
placing the HMOR treated by tetrapropylammonium hydroxide in N2And (3) carrying out heat treatment at 250 ℃ for 2 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 2
Drying the HMOR stone molecular sieve in vacuum at 100 ℃ to obtain dried HMOR;
placing the obtained 20 g of molecular sieve sample into a closed reaction kettle, adding 20 g of urea solution into the reaction kettle, and stirring for 0.5 hour at 90 ℃;
putting the HMOR molecular sieve after urea treatment in N2And (3) carrying out heat treatment at 250 ℃ for 2 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 3
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
a20 gram sample of the molecular sieve obtained above was placed in a closed reaction vessel. Adding 20 g of tetrapropylammonium hydroxide solution into another solution tank, heating to 50 ℃, and adding N2Introducing into a solution tank of tetrapropylammonium hydroxide, and utilizing N2The adsorbed tetrapropylammonium hydroxide vapor was passed into a closed reactor of molecular sieves for 10 minutes.
Placing the HMOR zeolite molecular sieve saturated in adsorption in N2And (3) carrying out heat treatment at 250 ℃ for 4 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 4
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
a20 gram sample of the molecular sieve obtained above was placed in a closed reaction vessel. Adding 20 g of urea solution into another solution tank, heating to 90 ℃, and adding N2Introducing into a urea solution tank, and using N2The adsorbed aqueous urea vapor was passed into a closed reactor of molecular sieves for 10 minutes.
Placing the HMOR zeolite molecular sieve saturated in adsorption in N2And (3) carrying out heat treatment at 250 ℃ for 4 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 5
Drying the HMOR stone molecular sieve in vacuum at 100 ℃ to obtain dried HMOR;
placing the obtained 20 g of molecular sieve sample into a closed reaction kettle, adding 20 g of lutidine solution into the reaction kettle, and stirring for 0.5 hour at 90 ℃;
placing the HMOR molecular sieve after the lutidine treatment in N2And (3) carrying out heat treatment at 250 ℃ for 2 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 6
Drying the HMOR molecular sieve in vacuum at 100 ℃ to obtain a dried HMOR molecular sieve;
a20 gram sample of the molecular sieve obtained above was placed in a closed reaction vessel. Adding 20 g of lutidine solution into another solution tank, heating to 50 ℃, and adding N2Introducing dimethyl pyridine into a solution tank, and utilizing N2The adsorbed lutidine vapor was passed into a molecular sieve closed reactor for 10 minutes.
Placing the HMOR zeolite molecular sieve saturated in adsorption in N2And (3) carrying out heat treatment at 250 ℃ for 4 hours in the atmosphere to obtain the modified HMOR molecular sieve catalyst.
Comparative example 7
The sample in comparative example 1 was the HMOR molecular sieve obtained in example 1 by vacuum drying only at 100 ℃.
FIG. 1 is an XRD pattern of HMOR molecular sieves prepared separately for examples 1, 3 and comparative example 7 of the present invention; the comparison of XRD spectrograms shows that the peak shape of the modified HMOR molecular sieve is lower, and the crystallinity is lower, which shows that the alkali modification removes framework silicon to cause framework defects, so that the crystallinity of the molecular sieve is reduced, and the XRD spectrogram of the molecular sieve after the alkali modification is lower than that of the unmodified molecular sieve.
FIG. 2 is a graph showing N of HMOR molecular sieves prepared in examples 1 and 3 of the present invention and comparative example 7, respectively2Adsorption and desorption curves. From N2The adsorption and desorption curve shows that the curve type of the modified HMOR molecular sieve is changed from the original more typical type I adsorption type to type I and IV adsorption types, and the modified HMOR molecular sieve is in P/P0Obvious hysteresis loops appear between 0.3 and 0.8, which indicates that after the treatment of organic alkali, partial mesopores appear on the HMOR molecular sieve because the framework silicon is partially removed. In addition, due to mild organic alkali and urea modification, amorphous substances in the pore channels of the molecular sieve can be eliminated, so that the pore volume and the surface area are increased. Thus, the modified HMOR molecular sieve N2The adsorption and desorption curves show obvious hysteresis loops, and the adsorption strength is increased.
FIG. 3 is a plot of the pore size distribution of HMOR molecular sieves prepared separately for examples 1, 3 and comparative example 7 of the present invention; as can be seen from the figure, the pore size of the molecular sieve after alkali treatment is obviously increased. The increased pore volume can enhance diffusion of reaction intermediate species and reaction products, thus increasing reactant conversion and reducing side reactions.
FIG. 4 is a graph showing the channel acidity profiles of HMOR molecular sieves prepared in examples 1 and 3 of the present invention and comparative example 7, respectively; as can be seen from fig. 4, the acid content in the twelve-membered ring channels of the HMOR molecular sieve modified by the two-component base is completely deactivated. The quaternary ammonium hydroxide/urea and the nitrogen-containing heterocyclic compound have larger molecular dynamic diameter and can only be selectively combined with the acidity in the twelve-membered ring channel of the HMOR molecular sieve, so that the acidity in the channel is neutralized, and the acidity in the eight-membered ring channel with smaller HMOR is reserved. In the dimethyl ether carbonylation reaction, dimethyl ether and carbon monoxide are subjected to glycosylation reaction at an acid site in an eight-membered ring of the HMOR molecular sieve to generate a target product methyl acetate, and the acid site in a twelve-membered ring is subjected to a side reaction of catalyzing dimethyl ether to generate carbon deposition.
The catalyst is used for preparing methyl acetate by dimethyl ether carbonylation, and the reaction conditions are as follows: placing 0.5 g of molecular sieve in a fixed bed reactor, charging 3.0% DME/95.5% CO/1.5% Ar reaction gas to 1.5MPa, raising the reaction temperature to 220 ℃ at a space velocity of 5280mL (g.h)-1The reaction is carried out under the condition, and the conversion rate of dimethyl ether and the selectivity of the product methyl acetate MA are detected by an online gas phase. The catalytic activity curve of the catalyst prepared in example 1 for preparing methyl acetate by carbonylation of dimethyl ether is shown in fig. 5, the catalytic activity curve of the catalyst prepared in example 2 for preparing methyl acetate by carbonylation of dimethyl ether is shown in fig. 6, the catalytic activity curve of the catalyst prepared in comparative example 7 for preparing methyl acetate by carbonylation of dimethyl ether is shown in fig. 7, and it can be seen from fig. 5 to fig. 7 that the conversion rate of dimethyl ether and the service life of the catalyst are remarkably improved by the HMOR zeolite treated by the mixture of tetrapropylammonium hydroxide and lutidine.
The catalytic performance of the HMOR molecular sieves prepared in examples 1 to 4 and comparative examples 1 to 7, respectively, for the carbonylation of dimethyl ether was simultaneously examined under the same reaction conditions, and the results are shown in table 1:
TABLE 1HMOR molecular sieve dimethyl ether carbonylation catalytic performance
As can be seen from table 1, the HMOR molecular sieve modified by urea or quaternary ammonium hydroxide alone can increase the conversion of dimethyl ether due to the mild removal of framework Si, increase of pore volume and thus increase of mass transfer rate of the product. The magnitude of the increase in dimethyl ether conversion is slightly different due to the different treatment regimes and the basicity of urea and quaternary ammonium hydroxide. However, urea and quaternary ammonium hydroxide only increase pore volume and can not passivate acid sites generating carbon deposit, so that after a period of reaction, the activity is rapidly lost, and the conversion rate of dimethyl ether is reduced to about 10% after 50 hours of reaction. When the nitrogen-containing heterocyclic compound is used for modification alone, the nitrogen-containing heterocyclic ring can neutralize the acid sites of the twelve-membered ring in the HMOR molecular sieve, so that the generation amount of carbon deposition is greatly reduced, and the reaction life is remarkably prolonged. Although the dimethyl ether conversion efficiency can not be greatly improved after the molecular sieve modified by the nitrogen-containing heterocycle is modified, the molecular sieve still can keep higher catalytic activity after reacting for 50 hours. Meanwhile, the HMOR molecular sieve modified by the two components of urea and nitrogen-containing heterocycle or quaternary ammonium hydroxide and nitrogen-containing heterocycle has higher dimethyl ether conversion efficiency and more stable service life. The urea or the quaternary ammonium base can construct mesopores, so that the mass transfer efficiency is increased, and meanwhile, the nitrogen-containing heterocycle can selectively passivate acid sites which are easy to generate carbon deposition, so that the double-component base modified HMOR molecular sieve can simultaneously improve the dimethyl ether conversion efficiency and prolong the service life of the catalyst, and can still maintain higher catalytic efficiency after reacting for 50 hours.
Claims (5)
1. A modification method for simultaneously improving the activity and the service life of an HMOR molecular sieve catalyst for carbonylation of dimethyl ether is characterized by comprising the following steps:
(1) drying the HMOR molecular sieve in vacuum at the temperature of 100-300 ℃ to obtain the dried HMOR molecular sieve;
(2) putting the HMOR molecular sieve dried in the step (1) into a mixed solution of quaternary ammonium hydroxide and nitrogen-containing heterocyclic compound bi-component organic mixed base, and stirring for 0.1-2 hours at 25-50 ℃, wherein the mass ratio of the quaternary ammonium hydroxide to the nitrogen-containing heterocyclic compound is 1: 0.2;
or putting the HMOR molecular sieve dried in the step (1) into a mixed solution of urea and a nitrogen-containing heterocyclic compound bi-component organic mixed alkali, and stirring for 0.1-2 hours at 40-95 ℃, wherein the mass ratio of the urea to the nitrogen-containing heterocyclic compound is 1: 0.2;
or introducing nitrogen into a mixed solution of quaternary ammonium base and nitrogen-containing heterocyclic compound bi-component organic mixed base, placing the dried HMOR molecular sieve obtained in the step (1) in a container, heating to 25-100 ℃, introducing N2Adsorbed quaternary ammonium base and nitrogen-containing heterocyclic compound double groupsMixing organic mixed base steam, wherein the mass ratio of the quaternary ammonium base to the nitrogen-containing heterocyclic compound is 1: 0.2;
or introducing nitrogen into a mixed solution of urea and a nitrogen-containing heterocyclic compound bi-component organic mixed base, placing the dried HMOR molecular sieve obtained in the step (1) in a container, heating to 40-90 ℃, introducing N2The method comprises the following steps of (1) adsorbing two-component organic mixed alkali steam of urea and a nitrogen-containing heterocyclic compound, wherein the mass ratio of the urea to the nitrogen-containing heterocyclic compound is 1: 0.2;
(3) and (3) placing the HMOR molecular sieve adsorbing the two-component alkali solution in an inert atmosphere, and carrying out heat treatment at the temperature of 100 ℃ and 400 ℃ for 2 hours to obtain the HMOR molecular sieve catalyst modified by the two-component alkali substance.
2. The modification method for improving the activity and the service life of the HMOR molecular sieve catalyst for carbonylation of dimethyl ether simultaneously according to claim 1, wherein in the step (2), the mass ratio of the HMOR molecular sieve to the two-component organic mixed base of the quaternary ammonium base and the nitrogen-containing heterocyclic compound is 0.5-5: 1.
3. the modification method for improving the activity and the service life of the HMOR molecular sieve catalyst for carbonylation of dimethyl ether simultaneously according to claim 1, wherein in the step (2), the mass ratio of the HMOR molecular sieve to the two-component organic mixed base of urea and the nitrogen-containing heterocyclic compound is 0.5-5: 1.
4. the modified method for simultaneously improving the activity and the service life of the HMOR molecular sieve catalyst for the carbonylation of dimethyl ether according to any one of claims 1 to 3, wherein in the step (2), the quaternary ammonium hydroxide is tetrapropylammonium hydroxide or tetraethylammonium hydroxide.
5. The modification method for improving the activity and the service life of the HMOR molecular sieve catalyst for carbonylation of dimethyl ether simultaneously according to any one of claims 1 to 3, wherein in the step (2), the nitrogen-containing heterocyclic compound is any one or more of lutidine, diaminopyridine and piperidine.
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| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| WO2010130973A2 (en) * | 2009-05-14 | 2010-11-18 | Bp Chemicals Limited | Carbonylation process |
| CN107376987A (en) * | 2016-05-16 | 2017-11-24 | 天津大学 | Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst and its application in methanol/dimethyl ether carbonylation |
| CN111514925A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Catalyst for co-production of methyl acetate and acetone from dimethyl ether, preparation method and application thereof |
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| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| WO2010130973A2 (en) * | 2009-05-14 | 2010-11-18 | Bp Chemicals Limited | Carbonylation process |
| CN107376987A (en) * | 2016-05-16 | 2017-11-24 | 天津大学 | Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst and its application in methanol/dimethyl ether carbonylation |
| CN111514925A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Catalyst for co-production of methyl acetate and acetone from dimethyl ether, preparation method and application thereof |
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