CN117603051A - Process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol - Google Patents
Process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 308
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000005832 oxidative carbonylation reaction Methods 0.000 title claims abstract description 23
- 238000004821 distillation Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 239000010949 copper Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 238000003860 storage Methods 0.000 claims description 60
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 30
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000007670 refining Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- -1 compound diethyl carbonate Chemical class 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102000019034 Chemokines Human genes 0.000 description 1
- 108010012236 Chemokines Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of preparation of nonmetallic compound diethyl carbonate, in particular to a process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol, which adopts ethanol, CO and O 2 The N-doped carbon-loaded copper catalyst is used as a catalyst to accelerate the ethanol oxidative carbonylation reaction and is used as a filler to provide a mass transfer surface in the catalytic rectification process. The diethyl carbonate produced by the process has the advantages of high product purity, high yield, simple process, environment friendliness, no equipment corrosion and the like, and catalyzes the reactionThe method is carried out in one step with the rectification process, reduces the environmental pollution caused by the catalyst, simultaneously effectively reduces the production cost and the energy consumption, and highly accords with the green and environment-friendly chemical principle.
Description
Technical Field
The invention relates to the technical field of preparation of nonmetallic compound diethyl carbonate, in particular to a process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol.
Background
Diethyl carbonate (DEC) is an important downstream product of ethanol, and has attracted considerable attention because of its excellent biodegradability, low toxicity, good solubility, and the like. The molecule contains ethyl-C 2 H 5 ethoxy-OC 2 H 5 Carbonyl c=o and the like, and thus exhibits a versatile adjustable chemical reactivity, can be used as an important chemical synthesis intermediate, and is widely used as a solvent for nitrocellulose, natural and synthetic resins. More importantly, the DEC has the advantages of excellent dissolution performance, low viscosity, small dielectric constant, capability of being mixed and dissolved with various organic solvents such as alcohol, ether, ketoester and the like, and is widely applied to the lithium battery electrolyte industry. The electrolyte is the blood of the power battery, is prepared by preparing and canning lithium salt (solute), solvent and additive, and accounts for 6-8% of the cost of the power battery. The ion-exchange type power battery is an important carrier for ion transmission in the power battery, and has obvious influence on battery safety, cycle life, charge-discharge multiplying power, high-low temperature performance and energy density. The electrolyte additive adopts a mixed solvent system and mainly consists of various carbonates such as dimethyl carbonate (DMC, 30-40%), ethylene carbonate (EC, 20-30%), diethyl carbonate (DEC, 10-15%), ethylmethyl carbonate (EMC, 10-15%), propylene carbonate (PC, 5-10%). Whereas DEC has a better fuel/water distribution coefficient than DMC, a higher oxygen content (40.6%) than methyl tert-butyl ether (MTBE) (18.2%), thus having a broad development market and application prospect. In addition, because of the difficulty in sustainable supply of conventional fossil energy and the environmental problems caused thereby, although renewable energy sources such as solar energy, wind energy, water energy, and biomass energy can provide clean energy, power storage is considered to be a key innovative challenge in achieving the goal of renewable energy. Through development for over twenty years, china becomes the biggest world for producing and consuming lithium ion batteries in production technologyThe operation is in a tripod-standing situation with japan and korea. In recent years, under the support of policies, the new energy automobile industry in China rapidly develops, the production and sales amount is rapidly increased, the power battery demand is driven to be greatly expanded, the production and sales amount of new energy automobiles in 2022 year all year round respectively reach 705.8 ten thousand and 688.7 ten thousand, and the increase of 96.9% and 93.4% is respectively realized. At present, the lithium ion battery is widely applied to the fields of electronic communication and transportation due to the advantages of excellent energy density, cycle stability, charge-discharge efficiency and the like, and according to statistics, the global battery-level solvent requirement of 2025 is about 187.1 ten thousand tons, the Chinese battery-level solvent requirement is calculated according to the statistics, the speed is increased by 34.6% in the next 5 years, and the DEC requirement is 7.7 ten thousand tons. It is expected that the consumption of electrolyte solvents will continue to increase with the rapid development of new energy and power storage in the future, and DEC is a key raw material for electrolytes, and its market demand is rapidly rising.
The DEC can be classified into industrial grade and electronic grade according to purity, the industrial grade DEC can be used as solvent, additive of lubricating grease, organic synthetic raw material and common cleaning agent of lithium ion battery and electronic product, the electronic grade DEC can be used as electrolyte of high-end power battery, the purity is up to 99.999%, the water and ethanol content is lower than 2ppm, and no metal ion is detected. When the purity of the electrolyte additive is less than 99.9%, the decomposition potential is 4.6-4.9V, and the oxidation potential can be improved by more than 5.2V by improving the purity, and if the purity is further improved, the upper limit of the oxidation potential of DEC can be 6.7V. Thus, the purification of DEC is indispensable in the production process of a battery grade solvent, which is also one of the difficulties of the battery grade solvent production process.
At present, the main processes for synthesizing DEC (DEC) are transesterification, urea alcoholysis, ethanol and CO 2 The direct synthesis method and the ethanol oxidation-carbonylation method have the advantages of simple raw materials, short process flow, 85.7 percent of atomic utilization rate and the like, and are considered as the most promising green economic synthesis route. Particularly, the method has the advantages that the DEC byproducts produced by the ethanol oxidative carbonylation method are few, and the problems of complex subsequent purification process, large equipment investment and the like of the products can be avoided. In recent years, HMS, MCM-41 molecular sieve and active carbon are used as carriers to load CuCl catalystThe use of chemokines for the oxidative carbonylation of ethanol to DEC has been widely studied. Patent CN1379017a investigated the synergistic improvement of CO coordination ability of ethoxy to Cu in the catalytic process by adding electron donating ligands 1, 10-phenanthroline and N-methylimidazole to CuC1 catalyst, resulting in 13.6% ethanol conversion and 99.1% DEC selectivity. For another example, patent CN110252406B adopts mesoporous silica grafted by Schiff base as a carrier to load CuCl 2 -PdCl 2 The catalyst obtains higher DEC selectivity. Patent CN100500288C studied CuCl-CuCl 2 The pore diameter of the mesoporous carbon catalyst is single and adjustable, and the stable catalyst structure can inhibit the loss of the active component Cu to a certain extent. Also researchers obtained 18% DEC yields (energy. Fuel.,2002,16,177-181) over CuCl-PdCl-KOH/AC catalysts. Although the catalyst has a certain improvement on the activity of synthesizing DEC by oxidizing and carbonylating ethanol, the catalyst is used for loading CuCl/CuCl 2 The common problems of the catalyst are that the catalyst preparation scheme is slightly complicated, the catalyst life is short, the recovery is difficult and the reactor is corroded due to the loss of chloride ions in the reaction, which are also always problems in industrial production. Therefore, attention has recently been focused on chlorine-free copper-based catalysts to overcome the problem of catalyst deactivation caused by reactor corrosion and chlorine loss, mainly Cu-based catalysts and Cu-Pd-based co-catalysts, which are favored by a large number of researchers because of their low cost and excellent activity in the reaction, compared to expensive Pd-based catalysts.
Disclosure of Invention
The invention provides a process for synthesizing electronic grade diethyl carbonate by catalyzing and rectifying ethanol oxidative carbonylation, which aims to solve the problems of short service life, difficult recovery and reactor corrosion caused by complex catalyst preparation scheme and chlorine ion loss in the reaction in the existing method for synthesizing DEC.
The invention is realized by the following technical scheme: the process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol comprises the following steps:
step one: filling N-doped carbon-supported copper catalyst into a reaction rectifying towerThen, the ethanol as a reaction raw material is sent into a feed inlet of a reaction rectifying tower from a feed tank, so that the ethanol is fully contacted with the N-doped carbon-supported copper catalyst, and CO and O are introduced 2 Ethanol, CO and O in reactive distillation column 2 The method comprises the steps of starting to react under the action of a nitrogen-doped carbon-supported copper catalyst, wherein a reaction rectifying tower comprises target products of diethyl carbonate, byproduct acetaldehyde, ethyl formate and water which are generated, unreacted ethanol and a catalyst, an azeotrope of the unreacted ethanol, acetaldehyde and ethyl formate is extracted from the top of the reaction rectifying tower and enters a condenser, and a mixture of the generated diethyl carbonate, water and the catalyst is extracted from the bottom of the reaction rectifying tower and enters a diethyl carbonate separation and purification section;
step two: after the reaction is finished, non-condensable gases CO and O 2 The mixed gas is discharged from the top of the reactive rectifying tower and enters a gas separator, and is separated into CO and O 2 CO is conveyed to the carbon monoxide storage tank again through the pipeline, O 2 Is re-conveyed to an oxygen storage tank through a pipeline; the azeotrope of unreacted ethanol, acetaldehyde and ethyl formate extracted from the top of the reactive rectifying tower enters a condenser and then enters an ethanol rectifying tower for separation; after mixed liquid of acetaldehyde and ethyl formate is extracted from the top of the ethanol rectifying tower, the mixed liquid is sent into the rectifying tower to realize the separation of acetaldehyde and ethyl formate and is respectively sent to an acetaldehyde storage tank and an ethyl formate storage tank; ethanol extracted from the bottom of the ethanol rectifying tower is sent into an ethanol rectifying tower, and refined ethanol is sent into an ethanol storage tank;
the mixture of diethyl carbonate, water and catalyst extracted from the bottom of the reaction rectifying tower enters a filter press for solid-liquid separation, and the separated solid catalyst enters a catalyst storage tank and is sent to the reaction rectifying tower; delivering liquid-phase product diethyl carbonate and water to a mixed liquid storage tank, delivering the mixed liquid storage tank to a crude diethyl carbonate rectifying tower for water removal, taking water from the top of the crude diethyl carbonate rectifying tower, delivering the water into a water storage tank, taking dehydrated diethyl carbonate from the bottom of the crude diethyl carbonate rectifying tower, delivering the dehydrated diethyl carbonate into a diethyl carbonate refining and purifying tower for refining and purifying diethyl carbonate, taking electronic grade diethyl carbonate from the lateral line of the diethyl carbonate refining and purifying tower, and finally delivering the electronic grade diethyl carbonate into an electronic grade diethyl carbonate storage tank; and recycling the tower bottom extract of the diethyl carbonate refining and purifying tower to a mixed liquid storage tank for continuous treatment.
In particular, the reaction occurring in the reactive distillation column of step one is as follows:
the main reaction: 2CH 3 CH 2 OH + CO + 1/2O 2 = (CH 3 CH 2 O) 2 CO (DEC) + H 2 O
Side reaction: (1) CH (CH) 3 CH 2 OH + 1/2O 2 = CH 3 CHO (ACE)+ H 2 O
(2) CH 3 CH 2 OH + CO = HCOOCH 2 CH 3 (EF)
As a further improvement of the technical scheme of the invention, the theoretical plate number of the reactive rectifying tower is 90, wherein the plate number of the rectifying section is 35, the plate number of the reaction section is 30, the plate number of the stripping section is 25, the temperature of the reaction section is 110-160 ℃, the temperature of the tower top is 80 ℃, the temperature of the tower bottom is 130 ℃, the operating pressure is 0.1-5 mpa, and the reflux ratio is 3-9.
As a further improvement of the technical scheme of the invention, the carrier of the N-doped carbon-supported copper catalyst is an N-doped carbon material, wherein the N element accounts for 1.3% -9.7%, and the active component copper accounts for 5% -20%.
As a further improvement of the technical scheme of the invention, the mass ratio of the ethanol serving as a reaction raw material to the N-doped carbon-supported copper catalyst is 33:1-100:1, and the mass ratio of CO to O is 2 The molar ratio of the catalyst to the catalyst is 2:1-9:1, and the temperature of the reaction section of the reactive rectifying tower is 110-160 ℃.
As a further improvement of the technical scheme of the invention, the operating pressure of the ethanol rectifying tower is 0.1Mpa, the theoretical plate number is 20-50, the tower top temperature is 40-60 ℃, the tower bottom temperature is 80-100 ℃, and the reflux ratio is 2-5.
As a further improvement of the technical scheme of the invention, the operation pressure of the crude diethyl carbonate rectifying tower is 0.3Mpa, the theoretical plate number is 40, the reflux ratio is 2-7, the tower top operation temperature is 90-110 ℃, and the tower bottom operation temperature is 110-140 ℃.
As a further improvement of the technical scheme of the invention, the operation pressure of the diethyl carbonate refining and purifying tower is 0.4Mpa, the theoretical plate number is 45, the reflux ratio is 3-8, the tower top operation temperature is 90-105 ℃, and the tower bottom operation temperature is 110-135 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The process adopts ethanol, CO and O 2 The N-doped carbon-loaded copper catalyst is used as a catalyst to accelerate the ethanol oxidative carbonylation reaction and is used as a filler to provide a mass transfer surface in the catalytic rectification process. Because of the high coupling between the catalytic reaction and the rectification process, the reaction product can be continuously removed in the reaction process, thereby realizing the synthesis and purification of diethyl carbonate, and the catalytic rectification process has the advantages of high selectivity, high yield, low energy consumption and low investment. Meanwhile, the diethyl carbonate produced by the process has the advantages of high product purity, high yield, simple process, environmental protection, no equipment corrosion and the like, and the catalytic reaction and rectification process are performed in one step, so that the environmental pollution caused by the catalyst is reduced, the production cost and the energy consumption are effectively reduced, and the environment-friendly chemical principle is highly met.
(2) Compared with other synthesis processes, the process has the advantages of simple raw materials, high atomic utilization rate (85.7 percent) and simple production and purification processes, and in addition, the combination of a plurality of rectifying towers simultaneously realizes the rectification and purification of unreacted ethanol, the rectification and purification of target product diethyl carbonate and the rectification of byproduct water, acetaldehyde and ethyl formate, and CO and O after reaction 2 The ethanol can be separated by a gas separator for recovery, so that the production cost is effectively saved, the ethanol after rectification and purification can be continuously recycled as a reaction raw material, and the purity of the electronic grade diethyl carbonate prepared by the process can reach more than 99.999 percent.
(3) The N-doped carbon-supported copper catalyst is adopted in the process, the raw material of the N-doped carbon material is green, the preparation process is simple, and the doped nitrogen atoms provide sufficient anchoring sites for active species while increasing the surface defects of the carrier, so that the generation of a target product DEC is facilitated, few byproducts are easy to separate, and further the refining and purification of the DEC are greatly promoted.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic diagram of a process flow of preparing electronic grade DEC by catalytic distillation ethanol oxidative carbonylation according to the present invention.
In the figure, 1-a feed tank; 2-a reactive rectifying tower; 3-a condenser; 4-a gas separator; 5-a carbon monoxide storage tank; 6-an oxygen storage tank; 7-an ethanol rectifying tower; 8-a rectifying tower; 9-an ethanol refining tower; 10-an ethanol storage tank; 11-a filter press; 12-a catalyst storage tank; 13, a mixed liquor storage tank; 14-a crude diethyl carbonate rectifying tower; 15-a water storage tank; 16-diethyl carbonate refining and purifying tower; 17-an acetaldehyde storage tank; 18-ethyl formate storage tank; 19-electronic grade diethyl carbonate storage tank.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
The invention provides a specific embodiment of a process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol, which comprises the following steps:
step one: after the N-doped carbon-supported copper catalyst is filled in the reaction rectifying tower 2, the ethanol serving as a reaction raw material is sent into a feed inlet of the reaction rectifying tower 2 from a feed tank 1, so that the ethanol is fully contacted with the N-doped carbon-supported copper catalyst, and CO and O are introduced 2 Ethanol, CO and O in 2-phase reaction rectifying tower 2 The reaction starts under the action of a nitrogen-doped carbon-supported copper catalyst, target products diethyl carbonate, byproducts acetaldehyde, ethyl formate and water which are generated in the reaction rectifying tower 2, unreacted ethanol and catalyst are contained in the reaction rectifying tower 2, an azeotrope of the unreacted ethanol, acetaldehyde and ethyl formate which is extracted from the top of the reaction rectifying tower 2 enters a condenser 3, and a mixture of the diethyl carbonate, water and catalyst which is generated from the bottom of the reaction rectifying tower 2 enters a diethyl carbonate separation and purification section;
step two: after the reaction is finished, non-condensable gases CO and O 2 The mixed gas is discharged from the top of the reactive rectifying tower 2 and enters a gas separator 4, and is separated into CO and O 2 The CO is re-transported to the carbon monoxide storage tank 5,O via a pipeline 2 Is re-conveyed via a pipeline to an oxygen storage tank 6; the azeotrope of unreacted ethanol, acetaldehyde and ethyl formate extracted from the top of the reactive rectifying tower 2 enters a condenser 3 and then enters an ethanol rectifying tower 7 for separation; after mixed liquid of acetaldehyde and ethyl formate is extracted from the top of the ethanol rectifying tower 7, the mixed liquid is sent to a rectifying tower 8 to realize the separation of acetaldehyde and ethyl formate and is respectively sent to an acetaldehyde storage tank 17 and an ethyl formate storage tank 18; ethanol extracted from the bottom of the ethanol rectifying tower 7 is sent into an ethanol rectifying tower 9, and the refined ethanol is sent into an ethanol storage tank 10;
the mixture of diethyl carbonate, water and catalyst extracted from the bottom of the reaction rectifying tower 2 enters a filter press 11 for solid-liquid separation, and the separated solid catalyst enters a catalyst storage tank 12 and is sent to the reaction rectifying tower 2; the liquid-phase product diethyl carbonate and water are conveyed to a mixed liquid storage tank 13, then are conveyed to a crude diethyl carbonate rectifying tower 14 for water removal, water is extracted from the top of the crude diethyl carbonate rectifying tower 14 and is conveyed to a water storage tank 15, dehydrated diethyl carbonate extracted from the bottom of the crude diethyl carbonate rectifying tower 14 enters a diethyl carbonate refining and purifying tower 16 for refining and purifying diethyl carbonate, electronic grade diethyl carbonate is extracted from the lateral line of the diethyl carbonate refining and purifying tower 16, and finally enters an electronic grade diethyl carbonate storage tank 19; the bottom extract of the diethyl carbonate refining and purifying tower 16 is recycled to the mixed liquor storage tank 13 for continuous treatment.
The technology adopts a catalytic rectification method to catalyze the ethanol to continuously synthesize DEC by an oxidative carbonylation method, fills an N-doped carbon-supported copper catalyst into a reaction rectifying tower 2, then mixes and introduces ethanol, oxygen and carbon monoxide serving as reaction raw materials into the reaction rectifying tower 2, and reacts under the action of the N-doped carbon-supported copper catalyst to generate and obtain a liquid phase mixture of diethyl carbonate (DEC), ethanol (EtOH), acetaldehyde (ACE) and Ethyl Formate (EF). The catalytic distillation process can continuously carry out catalytic reaction and distillation separation in the same tower, and the solid catalyst is used as a catalyst to accelerate chemical reaction in the catalytic distillation process, is used as a filler or a tower internal part to provide a mass transfer surface, and can continuously remove reaction products in the reaction process, so that the catalytic distillation process has the advantages of high selectivity, high production capacity, high yield, low energy consumption, low investment and the like, and is a novel process for strengthening reaction and separation by coupling separation and reaction. Preferably, since the catalyst in this embodiment plays both a catalytic role and a surface mass transfer role in catalytic reaction rectification, the catalyst is packed so as to be in sufficient contact with the reactants to perform its catalytic role on the one hand, and so as to be easily separated for recycling the catalyst on the other hand, and the catalyst particles should be reasonably and effectively distributed in the reaction rectification column 2.
In one embodiment provided by the invention, the theoretical plate number of the reactive rectifying tower 2 is 90, and the feeding position of the mixed material flow is between the rectifying section and the reaction section, wherein the theoretical plate number of the rectifying section is preferably 35; the theoretical plate number of the reaction section is preferably 30, and the theoretical plate number of the stripping section is preferably 25. The rectifying section adopts structured packing, the reaction section adopts tower plates, the reaction rectifying tower is a pressure-variable rectifying tower, the operating pressure is 3Mpa, and the reflux ratio is 5. In this embodiment, the catalyst is extracted from the bottom of the reactive rectifying tower 2, the product water and diethyl carbonate enter a filter material chamber of the filter press 11, the mixture is made to enter the pores of the filter membrane by pre-pressing, then the solid catalyst is gradually compressed by using the pressure (0.6 Mpa) in the filter material chamber, the water and diethyl carbonate are removed, and then the catalyst obtained by the filter pressing is sent to the catalyst storage tank 12.
In another embodiment of the present invention, the carrier of the N-doped carbon-supported copper catalyst is an N-doped carbon material, wherein the N element accounts for 1.3% -9.7% and the active component copper accounts for 5% -20%. The mass ratio of the ethanol serving as a reaction raw material to the N-doped carbon-supported copper catalyst in the reaction rectifying tower 2 is 33:1-100:1, and the mass ratio of CO to O is 2 The molar ratio of (2) to (1) to (9) to (1), and the temperature of the reaction section of the reaction rectifying tower 2 is preferably 120 ℃; the pressure at the top of the column is preferably 3MPa; the temperature of the top of the column is preferably 80 ℃; the temperature of the tower kettle is preferably 130 ℃; the reflux ratio is preferably 5.
In one embodiment provided by the invention, the operating pressure of the ethanol rectifying tower 7 is 0.1Mpa, the theoretical plate number is preferably 40, the tower top temperature is preferably 50 ℃, the tower bottom temperature is preferably 90 ℃, and the reflux ratio is preferably 4. The ethanol rectifying tower 7 is an atmospheric rectifying tower and is used for purifying impurities in unreacted ethanol.
In another embodiment provided by the invention, the operation pressure of the crude diethyl carbonate rectifying tower 14 is 0.3Mpa, the theoretical plate number is preferably 40, the tower top operation temperature is preferably 100 ℃, the tower bottom operation temperature is preferably 130 ℃, and the reflux ratio is preferably 5. The crude diethyl carbonate rectifying tower 14 is an atmospheric rectifying tower.
In one embodiment provided by the invention, the diethyl carbonate refining and purifying column 16 is operated at a pressure of 0.4Mpa, a theoretical plate number of preferably 45, a reflux ratio of preferably 6, a column top operating temperature of preferably 100 ℃ and a column bottom operating temperature of 120 ℃. The diethyl carbonate refining and purifying tower 16 is an atmospheric rectifying tower, and the side line of the diethyl carbonate refining and purifying tower 16 is used for extracting diethyl carbonate products with mass fraction of more than 99.999%.
In this embodiment, carbon monoxide and oxygen in the carbon monoxide storage tank 5 and the oxygen storage tank 6 are circularly conveyed to the reaction rectifying tower 2, ethanol in the ethanol storage tank 10 is circularly conveyed to the feeding storage tank 1, and the N-doped carbon-supported copper catalyst in the catalyst storage tank 12 is recycled and filled into the reaction rectifying tower 2.
Preferably, the condensing medium of the condenser 3 is water, and the condensing temperature is 0-25 ℃. The gas separator 4 is provided with a pressure monitoring system and a membrane separator, so that oxygen and carbon monoxide can be rapidly separated and are input into a corresponding storage tank through a pipeline.
Specific embodiments of the present invention are described in detail below.
A process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol comprises the following steps:
step one: after the N-doped carbon-supported copper catalyst is filled in the reaction rectifying tower 2, the ethanol serving as a reaction raw material is sent into a feed inlet of the reaction rectifying tower 2 from a feed tank 1, so that the ethanol is fully contacted with the N-doped carbon-supported copper catalyst, and CO and O are introduced 2 The mol ratio of ethanol, carbon monoxide and oxygen is 21:5:1, and the mass ratio of ethanol to catalyst is 39.45:1, a step of; ethanol, CO and O in 2-phase reaction rectifying tower 2 The reaction starts under the action of a nitrogen-doped carbon-supported copper catalyst, target products of diethyl carbonate, by-product acetaldehyde, ethyl formate and water which are generated in the reaction rectifying tower 2, unreacted ethanol and catalyst are contained in the reaction rectifying tower, an azeotrope of the unreacted ethanol, the acetaldehyde and the ethyl formate which is extracted from the top of the reaction rectifying tower 2 enters a condenser 3, and a mixture of the diethyl carbonate, the water and the catalyst which is generated from the bottom of the reaction rectifying tower 2 enters a diethyl carbonate separation and purification section.
The specific preparation of the catalysts used in the examples is found in: chemical Engineering Journal 475 (2023) 146368.
The specific parameters of the reactive distillation column 2 are as follows:
ethanol, carbon monoxide and oxygen in the reactive rectifying tower 2 are subjected to ethanol oxidative carbonylation under the action of an N-doped carbon-supported copper catalyst, the reaction paths are two, and the ethanol is firstly subjected to O 2 Oxidation to ethoxy (CH) 3 CH 2 O) species, pathway one is CO insertion into CH 3 CH 2 Formation of ethyl ester group (CH) in O 3 CH 2 OCO），CH 3 CH 2 OCO is reacted with ethanol to produce DEC, and the second route is CH 3 CH 2 O firstly reacts with ethanol to generate diethoxy ((CH) 3 CH 2 O) 2 ) After which CO is inserted directly (CH 3 CH 2 O) 2 The DEC is specifically as follows, wherein (M) represents an active site that interacts with M species:
(CH 3 CH 2 O)* + O* = (CH 3 CH 2 O)*(OH)* (R1)
pathway 1 (CH) 3 CH 2 O)* + CO = (CH 3 CH 2 OCO)* (R2)
(CH 3 CH 2 OCO)* + (CH 3 CH 2 O)* = (DEC)* (R3)
Pathway 2 (CH) 3 CH 2 O)*(OH)*+CH 3 CH 2 O=(CH 3 CH 2 O) 2 * + H 2 O (R4)
(CH 3 CH 2 O) 2 * + CO = (DEC)* (R5)
(DEC)*=DEC + * (R6)
Due to O in the system 2 The presence of (2) ethanol oxidative carbonylation reaction is accompanied by side reaction to form acetaldehyde and ethyl formate as by-products, and water as by-products, and after the reaction, the reaction rectifying tower 2 contains unreacted ethanol, diethyl carbonate, water as by-products, acetaldehyde and ethyl formate, catalyst and non-condensable gases CO and O 2 。
Step two: after the reaction is finished, non-condensable gases CO and O 2 The mixed gas is discharged from the top of the reactive rectifying tower 2 and enters a gas separator 4, and is separated into CO and O 2 The CO is re-transported to the carbon monoxide storage tank 5,O via a pipeline 2 Is re-conveyed via a pipeline to an oxygen storage tank 6; the azeotrope of unreacted ethanol, acetaldehyde and ethyl formate extracted from the top of the reactive rectifying tower 2 enters a condenser 3 and then enters an ethanol rectifying tower 7 for separation; after mixed liquid of acetaldehyde and ethyl formate is extracted from the top of the ethanol rectifying tower 7, the mixed liquid is sent to a rectifying tower 8 to realize the separation of acetaldehyde and ethyl formate and is respectively sent to an acetaldehyde storage tank 17 and an ethyl formate storage tank 18; ethanol extracted from the bottom of the ethanol rectifying tower 7 is sent into an ethanol rectifying tower 9, and the refined ethanol is sent into an ethanol storage tank 10.
The specific parameters of the ethanol rectifying tower 7 are as follows:
the specific parameters of the rectifying column 8 are as follows:
specific parameters of the ethanol purification column 9 are as follows:
the mixture of diethyl carbonate, water and catalyst extracted from the bottom of the reaction rectifying tower 2 enters a filter press 11 for solid-liquid separation, and the separated solid catalyst enters a catalyst storage tank 12 and is sent to the reaction rectifying tower 2; the liquid-phase product diethyl carbonate and water are conveyed to a mixed liquid storage tank 13, then are conveyed to a crude diethyl carbonate rectifying tower 14 for water removal, water is extracted from the top of the crude diethyl carbonate rectifying tower 14 and is conveyed to a water storage tank 15, dehydrated diethyl carbonate extracted from the bottom of the crude diethyl carbonate rectifying tower 14 enters a diethyl carbonate refining and purifying tower 16 for refining and purifying diethyl carbonate, electronic grade diethyl carbonate is extracted from the lateral line of the diethyl carbonate refining and purifying tower 16, and finally enters an electronic grade diethyl carbonate storage tank 19; the bottom extract of the diethyl carbonate refining and purifying tower 16 is recycled to the mixed liquor storage tank 13 for continuous treatment.
The specific parameters of the crude diethyl carbonate rectification column 14 are as follows:
specific parameters of the diethyl carbonate purification column 16 are as follows:
the parameters of the refined diethyl carbonate product are shown in the following table:
the foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Although described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the embodiments, and they should be construed as covering the scope of the appended claims.
Claims (7)
1. The process for synthesizing the electronic grade diethyl carbonate by oxidative carbonylation of the catalytic distillation ethanol is characterized by comprising the following steps of:
step one: after the N-doped carbon-supported copper catalyst is filled in a reaction rectifying tower (2), the ethanol serving as a reaction raw material is sent into a feed inlet of the reaction rectifying tower (2) from a feed tank (1) so that the ethanol is fully contacted with the N-doped carbon-supported copper catalyst, and CO and O are introduced 2 Ethanol, CO and O in the reaction rectifying tower (2) 2 The reaction starts to take place under the action of the nitrogen-doped carbon-supported copper catalystThe rectification tower (2) comprises target products of diethyl carbonate, byproduct acetaldehyde, ethyl formate and water which are generated, unreacted ethanol and a catalyst, an azeotrope of the unreacted ethanol, the acetaldehyde and the ethyl formate which are extracted from the top of the reaction rectification tower (2) enters a condenser (3), and a mixture of the diethyl carbonate, the water and the catalyst which are generated from the bottom of the reaction rectification tower (2) enters a diethyl carbonate separation and purification section;
step two: after the reaction is finished, non-condensable gases CO and O 2 The mixed gas is discharged from the top of the reactive rectifying tower (2) and enters a gas separator (4), and is separated into CO and O 2 CO is conveyed to the carbon monoxide storage tank (5) again through the pipeline, O 2 Is re-conveyed to an oxygen storage tank (6) through a pipeline; the azeotrope of unreacted ethanol, acetaldehyde and ethyl formate which is extracted from the top of the reactive rectifying tower (2) enters a condenser (3) and then enters an ethanol rectifying tower (7) for separation; after mixed liquid of acetaldehyde and ethyl formate is extracted from the top of the ethanol rectifying tower (7), the mixed liquid is sent to the rectifying tower (8) to realize the separation of the acetaldehyde and the ethyl formate and is respectively sent to an acetaldehyde storage tank (17) and an ethyl formate storage tank (18); ethanol extracted from the bottom of the ethanol rectifying tower (7) is sent into an ethanol rectifying tower (9), and the refined ethanol is sent into an ethanol storage tank (10);
the mixture of diethyl carbonate, water and catalyst extracted from the bottom of the reaction rectifying tower (2) enters a filter press (11) for solid-liquid separation, and the separated solid catalyst enters a catalyst storage tank (12) and is sent to the reaction rectifying tower (2); delivering liquid-phase product diethyl carbonate and water to a mixed liquid storage tank (13), delivering the mixed liquid storage tank to a crude diethyl carbonate rectifying tower (14) for removing water, taking water out of the top of the crude diethyl carbonate rectifying tower (14) and delivering the water into a water storage tank (15), taking dehydrated diethyl carbonate out of the bottom of the crude diethyl carbonate rectifying tower (14), delivering the dehydrated diethyl carbonate into a diethyl carbonate refining and purifying tower (16) for refining and purifying the diethyl carbonate, taking electronic grade diethyl carbonate out of the lateral line of the diethyl carbonate refining and purifying tower (16), and finally delivering the electronic grade diethyl carbonate into an electronic grade diethyl carbonate storage tank (19); and recycling the bottom extract of the diethyl carbonate refining and purifying tower (16) to a mixed liquid storage tank (13) for continuous treatment.
2. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of ethanol by catalytic distillation according to claim 1, wherein the theoretical plate number of the reaction rectifying tower (2) is 90, wherein the plate number of a rectifying section is 35, the plate number of a reaction section is 30, the plate number of a stripping section is 25, the temperature of the reaction section is 110-160 ℃, the temperature of the tower top is 80 ℃, the temperature of the tower bottom is 130 ℃, the operating pressure is 0.1-5 mpa, and the reflux ratio is 3-9.
3. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of ethanol through catalytic distillation according to claim 1, wherein the carrier of the N-doped carbon-supported copper catalyst is an N-doped carbon material, wherein the N element accounts for 1.3% -9.7%, and the active component copper accounts for 5% -20%.
4. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of ethanol by catalytic distillation according to claim 1, wherein the mass ratio of the ethanol as a reaction raw material to the N-doped carbon-supported copper catalyst is 33:1-100:1, and the mass ratio of CO to O is 2 The molar ratio of (2) to (1) to (9) to (1).
5. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytic distillation ethanol according to claim 1, wherein the operating pressure of the ethanol distillation column (7) is 0.1Mpa, the theoretical plate number is 20-50, the tower top temperature is 40-60 ℃, the tower bottom temperature is 80-100 ℃, and the reflux ratio is 2-5.
6. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of catalytically rectifying ethanol according to claim 1, wherein the operation pressure of the crude diethyl carbonate rectifying tower (14) is 0.3Mpa, the theoretical plate number is 40, the reflux ratio is 2-7, the tower top operation temperature is 90-110 ℃, and the tower bottom operation temperature is 110-140 ℃.
7. The process for synthesizing electronic grade diethyl carbonate by oxidative carbonylation of ethanol through catalytic distillation according to claim 1, wherein the operation pressure of the diethyl carbonate refining and purifying tower (16) is 0.4Mpa, the theoretical plate number is 45, the reflux ratio is 3-8, the tower top operation temperature is 90-105 ℃, and the tower bottom operation temperature is 110-135 ℃.
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