CN113443988B - Process for removing olefin in carbonylation reaction process of dimethyl ether - Google Patents
Process for removing olefin in carbonylation reaction process of dimethyl ether Download PDFInfo
- Publication number
- CN113443988B CN113443988B CN202110880351.6A CN202110880351A CN113443988B CN 113443988 B CN113443988 B CN 113443988B CN 202110880351 A CN202110880351 A CN 202110880351A CN 113443988 B CN113443988 B CN 113443988B
- Authority
- CN
- China
- Prior art keywords
- dimethyl ether
- gas
- olefin
- carbonylation
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 372
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 88
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000008569 process Effects 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 57
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 230000006315 carbonylation Effects 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 84
- 239000000463 material Substances 0.000 claims description 44
- 238000011084 recovery Methods 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 229910052680 mordenite Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000004229 Alkannin Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002151 riboflavin Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004230 Fast Yellow AB Substances 0.000 description 3
- 239000004283 Sodium sorbate Substances 0.000 description 3
- 239000004234 Yellow 2G Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004172 quinoline yellow Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000004149 tartrazine Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- -1 carbon olefin Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and relates to a process for removing olefin from dimethyl ether in a raw material dimethyl ether and a carbonylation reaction byproduct olefin in a dimethyl ether carbonylation reaction process, in particular to a process for removing olefin in a dimethyl ether carbonylation reaction process. On the basis of the existing technological process for synthesizing methyl acetate by dimethyl ether carbonylation, other reaction raw materials are not additionally introduced, and under the condition of not changing the technological conditions of the main dimethyl ether carbonylation reaction, an olefin removal pre-reactor is connected in series in front of the main dimethyl ether carbonylation methyl acetate reactor, an olefin conversion catalyst is arranged in the pre-reactor, a small amount of olefin in the dimethyl ether raw materials and olefin generated by the carbonylation reaction can be converted into saturated alkane through the pre-reactor, the one-way efficiency of converting the olefin into the alkane reaches more than 99.9 percent, carbon deposition caused by the olefin on the surface of the carbonylation catalyst in the reaction process is effectively reduced, and the stability of the carbonylation reaction process in the whole main dimethyl ether carbonylation methyl acetate reactor is improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a process for removing olefin from dimethyl ether in a raw material dimethyl ether in a reaction process of synthesizing methyl acetate by carbonylation of dimethyl ether and removing olefin as a byproduct of carbonylation reaction.
Background
Dimethyl ether (DME) is an important chemical raw material, and can be used for developing a series of fine chemical products with wide application range and good market prospect, such as dimethyl ether for preparing olefin, dimethyl ether for preparing methyl acetate by carbonylation, dimethyl ether for preparing dimethyl carbonate by carbonylation and oxidation, dimethyl ether and ammonia for synthesizing dimethylamine, dimethyl ether and dimethyl carbonate for preparing dialkoxy hydrocarbon compounds, dimethyl ether and ethylene oxide for synthesizing a mixture of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, and the like, and has great industrial importance and development potential. In addition, dimethyl ether can be used as aerosol, refrigerant and automobile fuel.
There are mainly two synthesis routes for dimethyl ether, the first known as the direct process, as described in patent CN101402042B using synthesis gas (CO + H) 2 ) Through CuZnAlMg (O) -gamma-Al 2 O 3 The method is characterized in that two reactions of preparing methanol from synthesis gas and preparing dimethyl ether from methanol by dehydration are coupled in a reactor; the second method is called indirect method, the synthesis gas firstly synthesizes methanol, then the methanol is vaporized and carries out dehydration reaction on a solid acid catalyst to produce dimethyl ether, and the two reactions are respectively carried out in independent reactors. Because the direct method has short service life of the bifunctional catalyst and does not meet the industrialized conditions, the production of the dimethyl ether in China adopts an indirect method. However, when dimethyl ether is produced by an indirect method, a small amount of ethylene and propylene are by-produced, and because ethylene and propylene are dissolved in dimethyl ether and are difficult to separate, if dimethyl ether with high purity is obtained, the separation difficulty is high. For example, CN107056588B adopts a mode of increasing the reflux ratio of a rectifying tower and obtains the purity of 9 by a mode of side line extraction of a dimethyl ether rectifying tower9.9996 percent of dimethyl ether with aerosol level, but the amount of dimethyl ether discharged from the top of the dimethyl ether rectifying tower is very large, and the discharged dimethyl ether at the top of the tower is 0.473 ton for every 1 ton of 99.9996 percent dimethyl ether produced, so the material consumption and the cost for producing high-purity dimethyl ether are greatly increased.
The method for producing the ethanol by using the dimethyl ether as the raw material and synthesizing the methyl acetate through carbonylation and then hydrogenating the methyl acetate is a technical route with application prospect, and the method for producing the ethanol by using the technical route is obviously superior to the method for producing the ethanol by using the traditional corn fermentation method in the aspect of economy. In the process of synthesizing methyl acetate by carbonyl synthesis of dimethyl ether and carbon monoxide (CO), researches of Iglesia et al find that mordenite molecular sieve (H-MOR) is used as a catalyst to show unique catalytic effect (Angew. Chem. Int. Ed.,2006, 45, 1617-1620), but the stability of the catalyst is poor due to carbon deposition formed in the reaction process. The cause of carbon deposition Liu et al speculated from the characterization of mordenite molecular sieve catalysts after different reaction durations (Fuel, 2021,286, 119480) that dimethyl ether as a reactant adsorbed on the acidity of the catalyst surface and methyl acetate as a product first produced olefins (such as ethylene) during desorption, the produced olefins further polymerized on the catalyst surface to form Soft carbon (Soft Coke), and the Soft carbon condensed to form Hard carbon (Hard Coke). Subsequently, many researchers started with improvement of a preparation process of a dimethyl ether carbonylation catalyst, and promoted the stability of the carbonylation catalyst by changing the morphology of the catalyst and adjusting the acidity and alkalinity of the surface of the catalyst, for example, in patent CN111087002A, mordenite with an acicular stacking structure is prepared by a two-step gel method, so that the radial diffusion distance is shortened, the diffusion rate of reactants is accelerated, and carbon deposition is reduced while the number of axial catalyst active sites is ensured. In patent CN111792994A, the H-MOR molecular sieve is subjected to organic ammonium salt exchange treatment, so that the service life of the catalyst is prolonged. The patent CN109092348A adopts a microwave reaction preparation method, so that the nucleation time in the preparation of the molecular sieve is shortened, the crystal grains of the mordenite molecular sieve are controlled, the diffusion resistance is reduced, and the carbon deposition of the catalyst is reduced. In patent CN111068763A, cu and lanthanide are added to hydrogen mordenite molecules to reduce selectivity of by-product low carbon olefin and improve stability of the catalyst, but the modified catalyst cannot completely inhibit the production of low carbon olefin.
The improvement of the catalyst preparation process cannot solve the problem of carbon deposition on the surface of the catalyst during the reaction of olefin. Therefore, in order to reduce carbon deposition caused by olefin and improve the stability of the catalyst for synthesizing methyl acetate by carbonylation of dimethyl ether, two ways are available: (1) The olefin amount is controlled from the source, namely the olefin content in the raw material is reduced, and the side reaction of olefin generated in the carbonylation reaction process is reduced by improving the preparation process of the dimethyl ether carbonylation catalyst; (2) Secondly, olefin generated by side reaction is removed from the reaction system, and the accumulation amount of the olefin in the reaction effective gas is reduced.
The method for removing trace olefin, especially propylene, in dimethyl ether by the rectification method of patent CN107056588B has high material consumption and energy consumption. And the synthesis of methyl acetate by the carbonylation of dimethyl ether and carbon monoxide is an acid catalytic process, and the catalytic activity center is the B acid acidic site on the surface of the mordenite. However, it is found that the acid sites are both catalytic active sites and active sites causing carbon deposition, so that sufficient acid sites are necessary to ensure the activity of the catalyst, and side reactions to form olefins are difficult to avoid. Therefore, the removal of by-produced olefin from the reaction system during the carbonylation reaction by means of the above-mentioned route (2) is very necessary for improving the stability of the dimethyl ether carbonylation catalyst.
Disclosure of Invention
The invention aims to provide a process technology for removing olefin in dimethyl ether and carbonylation reaction byproduct olefin in the reaction process of dimethyl ether carbonylation synthesis methyl acetate, under the condition of not additionally introducing other reaction raw materials and not changing the process conditions of dimethyl ether carbonylation main reaction, an olefin removal pre-reactor is connected in series in front of a dimethyl ether carbonylation synthesis methyl acetate main reactor, an olefin conversion catalyst is arranged in the pre-reactor, a small amount of olefin in the dimethyl ether and the olefin generated by the carbonylation reaction byproduct can be converted into saturated alkane through the pre-reactor, the single-pass efficiency of converting the olefin into the alkane reaches over 99.9 percent, the carbon deposition of the olefin on the carbonylation surface in the reaction process is effectively reduced, and the stability of the carbonylation catalyst in the whole dimethyl ether carbonylation synthesis methyl acetate main reactor is improved.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a process technology for removing olefin in dimethyl ether in a raw material dimethyl ether and a carbonylation byproduct olefin in a reaction process of dimethyl ether carbonylation synthesis of methyl acetate is characterized in that an olefin removal pre-reactor and a heater are added in front of a carbonylation main reactor in a process flow of dimethyl ether carbonylation synthesis of methyl acetate, a catalyst is filled in the olefin removal pre-reactor, and the process technology comprises the following specific steps:
1) Carbon monoxide and hydrogen from outside the battery limits and unreacted circulating gas enter a gas buffer tank together, the mixed gas exchanges heat with the discharged material from the carbonylation main reactor through a gas preheater, and the preheated mixed gas is heated through a gas heater. The dimethyl ether is preheated by a dimethyl ether preheater after the raw material dimethyl ether from outside the battery limits and the unreacted dimethyl ether are mixed, and the preheated material flow is heated by the dimethyl ether heater.
2) The gas heated by the gas heater and the heated dimethyl ether are uniformly mixed by the mixer and then enter the olefin removal pre-reactor, an olefin hydrogenation catalyst is filled in the olefin removal pre-reactor, and the olefin in the mixed material reacts with the hydrogen in the mixed material under the action of the hydrogenation catalyst to be converted into saturated alkane.
3) The mixture without olefin is heated to the temperature required by carbonylation reaction by a heater, and then enters a carbonylation main reactor, the carbonylation main reactor is filled with a catalyst (such as modified mordenite molecular sieve) required by carbonylation reaction, dimethyl ether and carbon monoxide generate methyl acetate under the action of the carbonylation catalyst, and a small amount of olefin is produced as a byproduct.
4) The material from the main carbonylation reactor is recycled by a gas preheater and a dimethyl ether preheater in turn, enters a crude product cooler for cooling, the cooled material is subjected to gas-liquid separation in a gas-liquid separator, unreacted carbon monoxide and hydrogen are returned to a gas buffer tank through a gas circulation booster, and the discharge amount of purge gas is adjusted to maintain the stability of inert gas (mainly supplemented carbon monoxide and nitrogen content in hydrogen) in the circulating gas, and the discharged part is saturated alkane generated in an olefin removal pre-reactor.
The liquid phase material separated from the gas-liquid separator mainly contains methyl acetate and unreacted dimethyl ether, the liquid phase material is sent into a dimethyl ether recovery tower, dimethyl ether and methyl acetate are separated in the dimethyl ether recovery tower in a rectification mode, the dimethyl ether separated from the tower top enters a reflux tank of the dimethyl ether recovery tower after being cooled by a condenser at the tower top of the dimethyl ether recovery tower, part of the dimethyl ether flows back through a reflux pump of the dimethyl ether recovery tower, and the other part of the dimethyl ether returns to be mixed with supplemented fresh dimethyl ether; the solution containing methyl acetate is obtained from the bottom of the tower.
Preferably, the proportions of carbon monoxide, hydrogen and dimethyl ether in the recycle gas are regulated and maintained constant by the make-up and tail gas purge amounts.
Preferably, the catalyst contained in the olefin removal pre-reactor is a supported catalyst containing one or more of Pd, pt, rh and Ru, and the carrier is alumina.
Preferably, the reaction temperature in the olefin removal prereactor is 50 to 200 ℃, and the reaction temperature is preferably 80 to 120 ℃.
Preferably, the higher the hydrogen concentration in the circulating gas, the more favorable the hydrogenation reaction in the olefin removal prereactor is; however, too high a hydrogen concentration reduces the concentration of dimethyl ether and carbon monoxide in the recycle gas, thereby reducing the efficiency of the carbonylation reaction in the carbonylation main reactor. In order to promote the hydrogenation reaction in the olefin removal prereactor, improve the conversion rate of olefin and ensure the conversion efficiency of synthesizing methyl acetate by dimethyl ether and carbon monoxide carbonyl, the volume ratio of hydrogen to dimethyl ether in the circulating gas is controlled to be 1.2-1.0.
Compared with the prior art, the invention has the beneficial effects that:
on the basis of the existing technological process for synthesizing methyl acetate by dimethyl ether carbonylation, other reaction raw materials are not additionally introduced, and under the condition of not changing the technological conditions of the main dimethyl ether carbonylation reaction, an olefin removal pre-reactor is connected in series in front of the main dimethyl ether carbonylation methyl acetate reactor, an olefin conversion catalyst is arranged in the pre-reactor, a small amount of olefin in the dimethyl ether raw materials and olefin generated by the carbonylation reaction can be converted into saturated alkane through the pre-reactor, the one-way efficiency of converting the olefin into the alkane reaches more than 99.9 percent, carbon deposition caused by the olefin on the surface of the carbonylation catalyst in the reaction process is effectively reduced, and the stability of the carbonylation reaction process in the whole main dimethyl ether carbonylation methyl acetate reactor is improved.
Drawings
FIG. 1 is a process flow diagram of the carbonylation of dimethyl ether to synthesize methyl acetate
Fig. 2 is a schematic diagram of a process flow for the carbonylation of dimethyl ether with olefin removal to methyl acetate as described herein.
Wherein, the reference number V-101 in the figure: a gas buffer tank; e-101: a gas preheater; e-102: a gas heater; m-101: a mixer; e-103: a dimethyl ether preheater; e-104: a dimethyl ether heater; r-101: a carbonylation main reactor; e-105: a coarse product cooler; v-102: a gas-liquid separator; c-101: a gas circulation supercharger; t-101: a dimethyl ether recovery tower; e-106: a reboiler of the dimethyl ether recovery tower; e-107: a dimethyl ether recovery tower top condenser; v-103: a reflux tank of the dimethyl ether recovery tower; p-101: a reflux pump of the dimethyl ether recovery tower; r-201: an olefin removal pre-reactor; e-201: a heater.
The specific implementation mode is as follows:
a process for removing olefin and byproduct olefin from carbonylation reaction in dimethyl ether comprises the following steps:
1) Carbon monoxide, hydrogen and unreacted circulating gas enter a gas buffer tank together, the mixed gas exchanges heat with the discharged material from the carbonylation main reactor through a gas preheater, and the preheated mixed gas is heated through a gas heater; the dimethyl ether is preheated by a dimethyl ether preheater after being mixed with the unreacted dimethyl ether from the outside of the battery limits, and the preheated material flow is heated by the dimethyl ether heater;
2) The gas heated by the gas heater and the dimethyl ether heated by the dimethyl ether heater are uniformly mixed by the mixer and then enter the olefin removal pre-reactor, and the olefin in the mixed material reacts with the hydrogen in the mixed material under the action of the hydrogenation catalyst to be converted into saturated alkane;
3) Heating the mixture without olefin to the temperature required by carbonylation reaction by a heater, then feeding the mixture into a carbonylation main reactor, generating methyl acetate by dimethyl ether and carbon monoxide under the action of a carbonylation catalyst, and simultaneously generating a small amount of olefin as a byproduct;
4) The material from the carbonylation main reactor sequentially passes through a gas preheater and a dimethyl ether preheater to recycle partial heat, enters a crude product cooler to be cooled, the cooled material realizes gas-liquid separation in a gas-liquid separator, unreacted carbon monoxide and hydrogen return to a gas buffer tank through a gas circulation supercharger, and the content of inert gas in the circulating gas is kept stable through the discharge amount of purge gas, and the discharge part of saturated alkane generated in R-201 is discharged.
5) The liquid phase material separated from the gas-liquid separator mainly contains methyl acetate and unreacted dimethyl ether, the liquid phase material is sent into a dimethyl ether recovery tower, dimethyl ether and methyl acetate are separated in the dimethyl ether recovery tower in a rectification mode, the dimethyl ether separated from the tower top enters a reflux tank of the dimethyl ether recovery tower after being cooled by a condenser at the tower top of the dimethyl ether recovery tower, part of the dimethyl ether flows back through a reflux pump of the dimethyl ether recovery tower, and the other part of the dimethyl ether returns to be mixed with supplemented fresh dimethyl ether; the solution containing methyl acetate is obtained from the bottom of the tower.
Preferably, the proportions of carbon monoxide, hydrogen and dimethyl ether in the recycle gas are regulated and maintained constant by the make-up and tail gas purge amounts.
Preferably, the olefin removal pre-reactor is filled with a catalyst, the filled catalyst is a supported catalyst containing any one or more of Pd, pt, rh and Ru, and the carrier is alumina.
Preferably, the reaction temperature in the olefin removal pre-reactor is 50-200 ℃; it is further preferred that the reaction temperature in the olefin removal prereactor is from 80 to 120 ℃.
Preferably, the carbonylation main reactor R-101 is filled with a catalyst required for carbonylation, and the catalyst is a modified mordenite molecular sieve.
Preferably, the volume ratio of hydrogen to dimethyl ether in the recycle gas is 1.2-1.0.
Preferably, the once-through efficiency of the conversion of the olefin into the alkane by the process reaches more than 99.9%.
Preferably, the ethylene content is reduced to 0.09ppm and the propylene content is reduced to 0.05ppm by the process
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, which are intended to illustrate the present invention and not to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1:
28.0kmol/h (pressure 2MPa, purity 98V%, and nitrogen balance) of carbon monoxide and 2.8kmol/h (pressure 2MPa, purity 99.5V%, and nitrogen balance) of hydrogen from outside the battery limits and unreacted recycle gas enter a gas buffer tank (V-101), and the mixed gas is heated to 80 ℃ through a gas preheater (E-101) and a gas heater (E-102) in sequence. Raw material dimethyl ether 18.7kmol/h (pressure 2MPa, raw material dimethyl ether contains 23ppm of ethylene and 147ppm of propylene) from outside the battery limits is mixed with unreacted dimethyl ether and then is heated to 80 ℃ by a dimethyl ether preheater (E-103) and a dimethyl ether heater (E-104) in sequence. The two materials are uniformly mixed by a mixer (M-101) and then enter an olefin removal pre-reactor (R-201), and the material flow entering the R-201 contains 12.0v% of hydrogen, 10.0v% of dimethyl ether, 69.8v% of carbon monoxide, 247ppm of ethylene, 181ppm of propylene, and the balance of nitrogen and the like. Pd/Al is contained in R-201 2 O 3 The catalyst has a reaction pressure of 2MPa. After the R-201 reaction, the content of ethylene in the mixed material of the R-201 is 0.15ppm, and the content of propylene is 0.14ppm.
The material from R-201 is heated to 195 ℃ by a heater (E-201) and enters a carbonylation main reactor (R-101), the pressure is still maintained at 2MPa, and the molar ratio of hydrogen and dimethyl ether at the inlet of R-101 is 1.2. After the carbonylation reaction, the ethylene content in the material from R-101 was 270ppm, the propylene content was 197ppm, and the methyl acetate content was 4.9v%. After the material is cooled by an E-101, an E-103 and a crude product cooler (E-105) in sequence, unreacted carbon monoxide and hydrogen are returned to V-101 by a gas circulation supercharger (C-101) in a gas-liquid separator (V-102), the discharge amount of exhausted gas is controlled to be 14.0kmol/h, and the amount of inert gas nitrogen in the circulating gas is controlled to be maintained at 5.0V%.
The liquid phase material separated from the V-102 mainly contains methyl acetate and unreacted dimethyl ether, wherein the content of methyl acetate is 76.5wt%, the content of dimethyl ether is 16.1wt%, and the rest is by-products of carbonylation reaction such as methanol, acetic acid, acetone and the like. The liquid phase material is sent into a dimethyl ether recovery tower T-101, the dimethyl ether obtained by the separation at the tower top enters a reflux tank (V-103) of the dimethyl ether recovery tower after being cooled by a condenser (E-107) at the tower top of the dimethyl ether recovery tower, and part of the dimethyl ether flows back by a reflux pump (P-101) of the dimethyl ether recovery tower, and the other part of the dimethyl ether returns to be mixed with the supplemented fresh dimethyl ether; the solution containing 97.9wt% of methyl acetate is obtained from the bottom of the tower.
Example 2:
on the basis of example 1, the olefin removal reactor inlet problem was increased to 120 ℃. The make-up hydrogen in example 1 was reduced to 2.5kmol/h to adjust the molar ratio of hydrogen to carbon monoxide in the recycle gas to 1.0, and the olefin removal prereactor (R-201) was charged with Pd-Ru/Al 2 O 3 The catalyst and other conditions are unchanged, and after the R-201 reaction, the content of ethylene in the mixed material of the R-201 can be reduced to 0.09ppm, and the content of propylene can be reduced to 0.05ppm.
Example 3:
the process conditions were the same as in example 1, and the stability of the carbonylation reaction was indicated by the space-time yield of methyl acetate over time, i.e. the amount of methyl acetate produced per unit of catalyst per unit of time, based on the amount of catalyst charged in R-101.
Carbon monoxide from outside the battery limits 28.0kmol/h (pressure 2MPa, purity 98v%, remainder nitrogen)Gas) and hydrogen 2.8kmol/h (pressure 2MPa, purity 99.5V%, nitrogen in the rest) enter a gas buffer tank (V-101) together with unreacted circulating gas, and the mixed gas is heated to 80 ℃ through a gas preheater (E-101) and a gas heater (E-102) in sequence. Raw material dimethyl ether 18.7kmol/h (pressure 2MPa, raw material dimethyl ether contains 23ppm of ethylene and 147ppm of propylene) from outside the battery limits is mixed with unreacted dimethyl ether and then is heated to 80 ℃ by a dimethyl ether preheater (E-103) and a dimethyl ether heater (E-104) in sequence. The two materials are mixed uniformly by a mixer (M-101) and then enter an olefin removal pre-reactor (R-201), and Pd/Al is filled in the R-201 2 O 3 The catalyst has a reaction pressure of 2MPa.
The material from R-201 is heated to 195 ℃ by a heater (E-201) and enters a carbonylation main reactor (R-101), the pressure is still maintained at 2MPa, and the molar ratio of hydrogen and dimethyl ether at the inlet of R-101 is 1.2. After the carbonylation reaction, the material is sequentially cooled by an E-101, an E-103 and a crude product cooler (E-105), unreacted carbon monoxide and hydrogen are returned to the V-101 by a gas circulation booster (C-101) in a gas-liquid separator (V-102), the discharge amount of exhausted gas is controlled to be 14.0kmol/h, and the amount of inert gas nitrogen in the circulating gas is controlled to be maintained at 5.0V%.
The liquid phase material separated from V-102 mainly contains methyl acetate and unreacted dimethyl ether, the liquid phase material is sent into a dimethyl ether recovery tower T-101, the dimethyl ether separated from the tower top enters a reflux tank (V-103) of the dimethyl ether recovery tower after being cooled by a condenser (E-107) at the tower top of the dimethyl ether recovery tower, part of the dimethyl ether flows back through a reflux pump (P-101) of the dimethyl ether recovery tower, and part of the dimethyl ether returns to be mixed with supplemented fresh dimethyl ether; the methyl acetate content in the solution containing methyl acetate obtained from the tower kettle is analyzed after a period of time, and the result is shown in table 1; as can be seen from table 1, in the course of reaction, the dimethyl ether carbonylation catalyst can cause carbon deposition due to the polymerization of olefin on the surface of the catalyst, so that the performance of the catalyst is reduced, and the conversion rate of the reactant is reduced. Under the condition of unchanged reaction conditions, the yield of the product methyl acetate is gradually reduced.
Comparative example 1
The process flow is as in the flow of FIG. 1, i.e., based on the reaction conditions of example 1, except that R-201 and E-201 are not provided in the process flow.
28.0kmol/h (pressure 2MPa, purity 98V%, the rest is nitrogen) of carbon monoxide and 2.8kmol/h (pressure 2MPa, purity 99.5V%, the rest is nitrogen) of hydrogen from outside the battery compartment enter a gas buffer tank (V-101) together with unreacted circulating gas, and the mixed gas is heated to 195 ℃ through a gas preheater (E-101) and a gas heater (E-102) in sequence. Raw material dimethyl ether 18.7kmol/h (pressure 2MPa, raw material dimethyl ether contains 23ppm of ethylene and 147ppm of propylene) from outside the battery limits is mixed with unreacted dimethyl ether and then is heated to 195 ℃ by a dimethyl ether preheater (E-103) and a dimethyl ether heater (E-104) in sequence. The two materials are uniformly mixed by a mixer (M-101) and then enter a carbonylation main reactor (R-101), the pressure is still maintained at 2MPa, and the molar ratio of hydrogen to dimethyl ether at an inlet of the R-101 is 1.2. After the carbonylation reaction, the material is cooled by an E-101, an E-103 and a crude product cooler (E-105) in sequence, unreacted carbon monoxide and hydrogen are returned to the V-101 by a gas circulation booster (C-101) in a gas-liquid separator (V-102), the discharge amount of exhausted gas is controlled to be 14.0kmol/h, and the amount of inert gas nitrogen in the circulating gas is controlled to be maintained at 5.0V%.
The liquid phase material separated from V-102 mainly contains methyl acetate and unreacted dimethyl ether, the liquid phase material is sent into a dimethyl ether recovery tower T-101, the dimethyl ether separated from the tower top enters a reflux tank (V-103) of the dimethyl ether recovery tower after being cooled by a condenser (E-107) at the tower top of the dimethyl ether recovery tower, part of the dimethyl ether flows back through a reflux pump (P-101) of the dimethyl ether recovery tower, and part of the dimethyl ether returns to be mixed with supplemented fresh dimethyl ether; the methyl acetate-containing solution obtained from the bottom of the column was analyzed for the content of methyl acetate at intervals, and the results are shown in Table 1.
Example 4
The process conditions were identical to those of example 2, i.e. the ethylene content entering the inlet of the R-101 reactor was reduced to 0.09ppm and the propylene content to 0.05ppm by increasing the reaction temperature of R-201. The contents of methyl acetate in the bottom solution of the T-101 column were then analyzed at intervals, the results of which are shown in Table 1.
TABLE 1 comparison of the space-time yields of methyl acetate under different process conditions
It can be seen from example 3 and comparative example 1 that under the same reaction conditions, the olefin removal pre-reactor R-201 is added to convert the olefin generated by the carbonylation reaction and the olefin brought by the dimethyl ether into alkane through catalyst hydrogenation saturation, and the carbonylation reactor in the back-stage carbonylation reactor R-101 is protected, and the space-time yield of methyl acetate is taken as a reference index, and after the reaction of example 3 for 300 hours, the value of methyl acetate is reduced by 4.6% compared with that of the reaction for 10 hours. In contrast, in comparative example 1, the addition of the olefin removal pre-reactor R-201 was not increased, and after 48 hours of reaction, the value of methyl acetate was reduced by 8.8% compared with that of the reaction for 10 hours; after the reaction for 154 hours, the yield of the methyl acetate is reduced by half, and after the reaction for 300 hours, the yield of the methyl acetate is only 20.8 percent of that of the reaction for 10 hours.
As can be seen from the comparison between example 3 and example 4, in example 3, after 300 hours of reaction, the value of methyl acetate was reduced by 4.6% compared to that after 10 hours of reaction. Example 4 after 300 hours of reaction, the value of methyl acetate decreased by 0.75% compared to 10 hours of reaction. Thus, it is shown that the lower the olefin content in the feed to R-101, the slower the reduction in the yield of methyl acetate, i.e., the lower the olefin content, the more favorable the stable operation of the catalyst in R-101.
Claims (9)
1. A process for removing olefin in the carbonylation reaction process of dimethyl ether is characterized by comprising the following steps:
1) Carbon monoxide, hydrogen and unreacted circulating gas enter a gas buffer tank together, the mixed gas exchanges heat with the discharged material from the carbonylation main reactor through a gas preheater, and the preheated mixed gas is heated through a gas heater; the dimethyl ether is preheated by a dimethyl ether preheater after being mixed with the unreacted dimethyl ether from the outside of the battery limits, and the preheated material flow is heated by the dimethyl ether heater;
2) The gas heated by the gas heater and the dimethyl ether heated by the dimethyl ether heater are uniformly mixed by the mixer and then enter the olefin removal pre-reactor, and the olefin in the mixed material reacts with the hydrogen in the mixed material under the action of the hydrogenation catalyst to be converted into saturated alkane;
3) Heating the mixture without olefin to the temperature required by the carbonylation reaction by a heater, then feeding the mixture into a carbonylation main reactor, and generating methyl acetate by dimethyl ether and carbon monoxide under the action of a carbonylation catalyst and simultaneously generating a small amount of olefin as a byproduct;
4) The material from the carbonylation main reactor sequentially passes through a gas preheater and a dimethyl ether preheater to recycle partial heat, enters a crude product cooler to be cooled, the cooled material realizes gas-liquid separation in a gas-liquid separator, unreacted carbon monoxide and hydrogen return to a gas buffer tank through a gas circulation supercharger, and the content of inert gas in the circulating gas is kept stable through the discharge amount of purge gas, and the discharge part of saturated alkane generated in R-201 is discharged;
5) The liquid phase material separated from the gas-liquid separator mainly contains methyl acetate and dimethyl ether which is not completely reacted, the liquid phase material is sent into a dimethyl ether recovery tower, the dimethyl ether is separated from the methyl acetate in the dimethyl ether recovery tower in a rectification mode, the dimethyl ether separated from the tower top enters a reflux tank of the dimethyl ether recovery tower after being cooled by a condenser at the tower top of the dimethyl ether recovery tower, part of the dimethyl ether flows back through a reflux pump of the dimethyl ether recovery tower, and the other part of the dimethyl ether returns to be mixed with the supplemented fresh dimethyl ether; the solution containing methyl acetate is obtained from the bottom of the tower.
2. The process of claim 1, wherein: the proportion of carbon monoxide, hydrogen and dimethyl ether in the circulating gas is regulated and maintained stably through the supplement amount and the tail gas relief amount.
3. The process of claim 1, wherein: the olefin removal pre-reactor is filled with a catalyst, the loaded catalyst is a supported catalyst containing any one or more of Pd, pt, rh and Ru, and the carrier is alumina.
4. The process of claim 1 or 3, wherein: the reaction temperature in the olefin removal prereactor is 50-200 ℃.
5. The process of claim 1 or 3, wherein: the reaction temperature in the olefin removal prereactor is 80-120 ℃.
6. The process of claim 1, wherein: the carbonylation main reactor R-101 is filled with a catalyst required by carbonylation reaction, and the catalyst is a modified mordenite molecular sieve.
7. The process of claim 1 or 2, wherein: the volume ratio of hydrogen to dimethyl ether in the circulating gas is 1.2-1.0.
8. The process of any one of claims 1-3 and claim 6, wherein: by the process, the once-through efficiency of converting the olefin into the alkane reaches over 99.9 percent.
9. The process of claim 8, wherein: by the process, the content of ethylene is reduced to 0.09ppm, and the content of propylene is reduced to 0.05ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110880351.6A CN113443988B (en) | 2021-08-02 | 2021-08-02 | Process for removing olefin in carbonylation reaction process of dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110880351.6A CN113443988B (en) | 2021-08-02 | 2021-08-02 | Process for removing olefin in carbonylation reaction process of dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113443988A CN113443988A (en) | 2021-09-28 |
| CN113443988B true CN113443988B (en) | 2022-10-11 |
Family
ID=77818046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110880351.6A Active CN113443988B (en) | 2021-08-02 | 2021-08-02 | Process for removing olefin in carbonylation reaction process of dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113443988B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119617302B (en) * | 2025-02-17 | 2025-05-13 | 安徽碳鑫科技有限公司 | An energy-saving dimethyl ether high-efficiency vaporization mixing method using CO as carrier gas |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8703999B2 (en) * | 2012-03-27 | 2014-04-22 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst |
| CN107522618A (en) * | 2017-10-12 | 2017-12-29 | 中石化炼化工程（集团）股份有限公司 | Method of Dimethyl ether carbonylation and application thereof and consersion unit |
| CN107973716B (en) * | 2018-01-04 | 2020-05-12 | 西南化工研究设计院有限公司 | Method for synthesizing methyl acetate by dimethyl ether carbonyl |
| CN111068763B (en) * | 2018-10-18 | 2022-12-09 | 中国石油化工股份有限公司 | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and synthetic method of methyl acetate |
| CN110694679B (en) * | 2019-10-30 | 2023-04-18 | 上海绿强新材料有限公司 | EMT/FAU core-shell molecular sieve catalyst, and preparation method and application thereof |
-
2021
- 2021-08-02 CN CN202110880351.6A patent/CN113443988B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113443988A (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Ni/ADM: a high activity and selectivity to C2+ OH catalyst for catalytic conversion of synthesis gas to C1-C5 mixed alcohols | |
| EP0479780A4 (en) | Homogeneous catalyst formulations for methanol production | |
| CN100349839C (en) | Method for synthesising mixture of methanol and dimethyl ether from syngas | |
| AU602438B2 (en) | One-step process for dimethyl ether synthesis utilizing a liquid phase reactor system | |
| CN113443988B (en) | Process for removing olefin in carbonylation reaction process of dimethyl ether | |
| CN104926657B (en) | The method of oxalate gas phase hydrogenation synthesizing alcohol acid esters | |
| US8398728B2 (en) | Process for making a composition comprising at least two different dialkyl ethers | |
| CN114163333B (en) | Method for synthesizing methyl ethyl carbonate in one step | |
| CN101830776B (en) | Method for synthesizing ethanol | |
| CN114984991A (en) | g-C 3 N 4 Preparation method of modified hydrotalcite catalyst and application of modified hydrotalcite catalyst in condensation reaction of furfural and cyclic ketone | |
| CN103570485A (en) | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO | |
| CN112661618B (en) | Copper catalysis preparation method of cyclopentanone | |
| CN109956845A (en) | A kind of propylene polymerization prepares the process of nonene | |
| CN101289376B (en) | Process for synthesizing 3,3-dimethyl-2-butanone | |
| CN115557829B (en) | Method for co-producing methanol and ethanol from synthesis gas | |
| CN105431406A (en) | Method for producing alpha-hydroxycarboxylic acid esters | |
| CN112979463B (en) | Method for synthesizing ester by catalytic esterification of ionic liquid | |
| US12036538B2 (en) | Molecular sieve catalyst, preparation method therefor, and application thereof | |
| CN116874349B (en) | Method for preparing 2, 2-dimethylolbutyraldehyde and trimethylolpropane | |
| KR102055927B1 (en) | Process for preparing acrolein | |
| KR20140045240A (en) | Preparation method of ethanol through synthesis gas using a ferrieirite catalyst | |
| CN112661619B (en) | Method for preparing cyclopentanone | |
| CN109824510A (en) | A kind of preparation method of ethyl acetate | |
| CN118002169B (en) | Catalyst for catalytic conversion of furfuryl alcohol into 1, 5-pentanediol, preparation method and application | |
| CN119504553B (en) | Method and system for co-producing N-methylaniline and N-methylindole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |