CN107999127B - Catalyst for preparing methyl acetate by methanol one-step method and application - Google Patents
Catalyst for preparing methyl acetate by methanol one-step method and application Download PDFInfo
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- CN107999127B CN107999127B CN201711210770.9A CN201711210770A CN107999127B CN 107999127 B CN107999127 B CN 107999127B CN 201711210770 A CN201711210770 A CN 201711210770A CN 107999127 B CN107999127 B CN 107999127B
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- catalyst
- methyl acetate
- rhodium
- methanol
- iodide
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 35
- 239000010948 rhodium Substances 0.000 claims abstract description 35
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- GYEQLVFBKDAMHD-UHFFFAOYSA-N 2-ethenylmorpholine Chemical compound C=CC1CNCCO1 GYEQLVFBKDAMHD-UHFFFAOYSA-N 0.000 claims description 3
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical group C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- -1 transition metal salt Chemical class 0.000 abstract description 5
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002952 polymeric resin Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PCALEDHRQVKVRM-UHFFFAOYSA-N carbonyl diiodide;rhodium Chemical compound [Rh].IC(I)=O PCALEDHRQVKVRM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Aethyl-cyclopentan Natural products CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AOZUYISQWWJMJC-UHFFFAOYSA-N acetic acid;methanol;hydrate Chemical compound O.OC.CC(O)=O AOZUYISQWWJMJC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- BNCGHLKQLVJQCW-UHFFFAOYSA-N iodomethane;methyl acetate Chemical compound IC.COC(C)=O BNCGHLKQLVJQCW-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical class [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J31/0231—Halogen-containing 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
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst system for preparing methyl acetate by a methanol one-step method and application thereof, and the catalyst system has high selectivity and good stability. The catalyst system of the invention uses macromolecular resin containing nitrogen atoms as a carrier, loads metal rhodium and an accelerant to obtain the catalyst, uses iodide as a cocatalyst, and uses the accelerant as a transition metal salt. The invention also discloses a preparation method of the catalyst for preparing methyl acetate from methanol, which comprises the following steps: and (2) preparing a carrier resin, and reacting rhodium triiodide, a transition metal salt and the carrier resin prepared in the step (1) in a solvent and carbon monoxide atmosphere to obtain the high-molecular heterogeneous rhodium catalyst. The production of methyl acetate is completed by adopting the heterogeneous rhodium catalyst one-step method, the solid catalyst and the product are simple to separate, the entrainment loss of rhodium in the liquid rhodium catalyst in the homogeneous oxo synthesis reaction is avoided, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a catalyst for preparing methyl acetate by a methanol one-step method and application thereof.
Background
Methyl acetate has wide industrial application, is a raw material for producing acetic anhydride by carbonylation and preparing ethanol by hydrogenation, and the ethanol is a large chemical product, is widely used in the fields of fuels, solvents and the like, and has strong social demand. The methyl acetate hydrogenation method is used for replacing the fermentation method to produce the ethanol, so that a large amount of grains can be saved. Methyl acetate is also a good solvent and is used for replacing acetone, butanone, ethyl acetate, cyclopentane and the like. In 2005, eastman company in the united states replaced acetone solvent with methyl acetate, which was non-toxic and not a limited organic pollutant discharge, and could meet the new environmental standards of paint, ink, resin, and adhesive factories, and was increasingly sought by people.
The main production method of methyl acetate is that methanol is firstly carbonylated to synthesize acetic acid, and then the acetic acid and methanol are esterified under the action of strong acid catalyst to obtain the product. The method is mature in technology, but the process flow is complicated, high in energy consumption, large in investment and uneconomical; usually, sulfuric acid is used as a catalyst, so that the requirement on materials is high and the pollution is large.
Disclosure of Invention
Aiming at the problems, the invention provides a catalyst system for preparing methyl acetate by a methanol one-step method, which has high selectivity and good stability.
The invention also aims to provide a preparation method of the catalyst for preparing methyl acetate by using the methanol one-step method.
The invention also aims to provide application of the catalyst system for preparing methyl acetate by the methanol one-step method.
The technical scheme adopted by the invention is as follows:
the catalyst system for preparing methyl acetate by using the methanol one-step method is characterized in that a macromolecular resin containing nitrogen atoms is used as a carrier, metal rhodium and an accelerant are loaded to obtain the catalyst, iodide is used as a cocatalyst, and the accelerant is a transition metal salt.
Further, the nitrogen atom-containing polymer resin is a morpholine group-containing polymer resin.
Further, the nitrogen atom-containing polymer resin is a vinyl morpholine group-containing polymer resin.
Further, the iodide is selected from at least one of methyl iodide, hydroiodic acid, lithium iodide, sodium iodide, potassium iodide, cesium iodide, or nickel iodide.
Further, the transition metal salt is selected from one or more of metal salts of ruthenium, osmium, nickel, cobalt, platinum, palladium, zinc, cadmium, mercury, manganese, vanadium, titanium, gallium, indium, thallium, tungsten, copper, aluminum, tin, and antimony.
Further, the molar ratio of the promoter to rhodium is from 0.3:1 to 30: 1.
Further, the mass percentage of the cocatalyst is 1-30% based on 100% of the catalyst system.
Further, the mass percentage of the cocatalyst is 3-20% based on 100% of the catalyst system.
The preparation method of the catalyst comprises the following steps:
step 1: preparing a carrier resin: carrying out polymerization reaction on 2-vinyl morpholine or 4-vinyl pyridine and p-divinylbenzene under the action of an azodiisobutyronitrile catalyst to obtain carrier resin;
step 2: and (2) reacting rhodium triiodide, a transition metal salt and the carrier resin prepared in the step (1) in the atmosphere of a solvent and carbon monoxide to obtain the high-molecular heterogeneous rhodium catalyst.
The catalyst system is used for producing methyl acetate by a heterogeneous process one-step method, and the reaction equation is as follows: 2CH3OH+CO→CH3COOCH3+H2O。
Compared with the prior art, the invention has the following beneficial effects:
the production of methyl acetate is completed by adopting the heterogeneous rhodium catalyst one-step method, the solid catalyst and the product are simple to separate, the entrainment loss of rhodium in the liquid rhodium catalyst in the homogeneous oxo synthesis reaction is avoided, and the production cost is reduced.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification (including any accompanying claims, abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
Preparation of the catalyst of the invention.
The preparation method of the rhodium-loaded high-molecular heterogeneous catalyst comprises the following steps:
preparation of the carrier resin: taking ethanol as a solvent, and carrying out polymerization reaction on 2-vinyl morpholine and p-divinylbenzene with the molar ratio of 1:1 under the action of an azobisisobutyronitrile catalyst with the mass percentage of 0.7% at the temperature of 90 ℃ at 3MP to obtain the carrier resin.
And (3) carrying out reaction on the carrier resin, rhodium triiodide and ammonium metatungstate in an acetic acid solvent and carbon monoxide atmosphere to obtain the high-molecular heterogeneous rhodium catalyst.
The mass percentage of rhodium in the prepared high-molecular heterogeneous rhodium catalyst is 0.7 percent, and the molar ratio of rhodium to tungsten is 2: 1.
Example 2
Preparation of the catalyst of the invention.
The preparation method of the rhodium-loaded high-molecular heterogeneous catalyst comprises the following steps: using acetic acid as a solvent, and carrying out polymerization reaction on 4-vinyl morpholine and p-divinylbenzene with a molar ratio of 2:1 under the action of an azobisisobutyronitrile catalyst with a mass percentage of 0.9% at 2MP and 85 ℃ to obtain the carrier resin. And (3) carrying out reaction on the carrier resin, rhodium triiodide and stannous chloride in the presence of a solvent of acetic acid and carbon monoxide to obtain the high-molecular heterogeneous rhodium catalyst. The mass percentage of rhodium in the prepared high-molecular heterogeneous rhodium catalyst is 0.5 percent, and the molar ratio of rhodium to tin is 3: 1.
Example 3
A rhodium catalyst prepared in example 1 was added to a 250 ml zirconium kettle in an amount of 800ppm in terms of rhodium, followed by addition of methanol, methyl iodide, water and acetic acid in the composition shown in Table I, substitution with CO was performed 3 times, the kettle cover was closed, CO was introduced thereinto, and the reaction was carried out for 20 minutes under conditions of a stirring rotation speed of 450rpm, a pressure of 3.0MPa and a temperature of 180 ℃ to obtain a product liquid. The mass percentages of the components of the raw material liquid and the product liquid are shown in the table I. The yield of the product methyl acetate is 98.8 percent calculated by methanol, and the loss rate of rhodium is less than 0.1 percent.
| Methanol | Acetic acid | Water (W) | Methyl iodide | Acetic acid methyl ester | |
| Raw material liquid% | 19.10 | 49.02 | 9.01 | 22.87 | 0 |
| Product liquor% | 1.07 | 41.47 | 15.01 | 20.92 | 21.53 |
Example 4
This example is a comparative example.
For comparison purposes, the conditions were the same as in example 3 except that rhodium carbonyl iodide was used as the catalyst and no support resin and metal promoter were added.
The yield of the methyl acetate product is 98.2 percent by methanol. After the rhodium catalyst and the product liquid are evaporated and separated, the loss rate of rhodium is more than 55 percent.
Example 5
This example is a comparative example.
For comparison purposes, the conditions were the same as in example 3 except that the catalyst was rhodium carbonyl iodide supported on a support resin and no metal promoter was added.
The yield of the methyl acetate product is 98.7 percent calculated by methanol. After the rhodium catalyst is separated from the product liquid, the loss rate of rhodium is more than 2 percent.
Example 6
This example is a comparative example.
For comparison purposes, the conditions were the same as in example 3 except that the catalyst used rhodium carbonyl iodide and the metal promoter and no support resin was added.
The yield of the product methyl acetate is 99.1 percent calculated by methanol, and the loss rate of rhodium is more than 6 percent after the rhodium catalyst and the product liquid are evaporated and separated.
By observing and analyzing the technical process and the result of the embodiment, the rhodium catalyst shows good catalytic activity in the reaction of preparing methyl acetate from methanol, and the loss rate of rhodium is small.
The invention is not limited to the embodiments described above but extends to any novel feature or any novel combination of features disclosed herein and any novel method or process steps or any novel combination of features disclosed herein.
Claims (5)
1. The application of the catalyst system for preparing methyl acetate by the methanol one-step method is characterized in that: the catalyst system is used for producing methyl acetate by a one-step method through a heterogeneous process, and the reaction equation is as follows:
2CH3OH+CO→CH3COOCH3+H2O；
the catalyst system takes macromolecular resin containing nitrogen atoms as a carrier, metal rhodium and an accelerant are loaded to obtain the catalyst, an iodide is taken as a cocatalyst, the accelerant is stannous chloride, and the macromolecular resin containing the nitrogen atoms is macromolecular resin containing vinyl morpholine groups;
the catalyst system is directly added into a zirconium kettle for catalytic reaction;
the preparation method of the catalyst comprises the following steps:
step 1: preparing a carrier resin: carrying out polymerization reaction on 2-vinyl morpholine and p-divinylbenzene under the action of an azodiisobutyronitrile catalyst to obtain carrier resin;
step 2: and (2) reacting rhodium triiodide, an accelerant and the carrier resin prepared in the step (1) in an acetic acid and carbon monoxide atmosphere to obtain the high-molecular heterogeneous rhodium catalyst.
2. The application of the catalyst system for preparing methyl acetate by the methanol one-step method according to claim 1 is characterized in that: the iodide is at least one selected from methyl iodide, hydroiodic acid, lithium iodide, sodium iodide, potassium iodide, cesium iodide and nickel iodide.
3. The application of the catalyst system for preparing methyl acetate by the methanol one-step method according to claim 2 is characterized in that: the molar ratio of the promoter to rhodium is 0.3:1-30: 1.
4. The application of the catalyst system for preparing methyl acetate by the methanol one-step method according to claim 3 is characterized in that: the raw materials for preparing the methyl acetate from the methanol comprise methanol, water and acetic acid, wherein the total mass of the raw materials and the cocatalyst is 100%, and the mass percentage of the cocatalyst is 1-30%.
5. The application of the catalyst system for preparing methyl acetate by the methanol one-step method according to claim 4 is characterized in that: the mass percentage of the cocatalyst is 3-20%.
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| CN106316846B (en) * | 2016-08-26 | 2018-12-25 | 西南化工研究设计院有限公司 | A kind of production method of methyl acetate |
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