CN115894234A - Synthetic method of dimethyl succinate - Google Patents
Synthetic method of dimethyl succinate Download PDFInfo
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- CN115894234A CN115894234A CN202211385593.9A CN202211385593A CN115894234A CN 115894234 A CN115894234 A CN 115894234A CN 202211385593 A CN202211385593 A CN 202211385593A CN 115894234 A CN115894234 A CN 115894234A
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Abstract
The application provides a method for synthesizing dimethyl succinate, which comprises the following steps: mixing a mixed gas containing inert gas, carbon monoxide, ethylene and methyl nitrite with a halogen-containing activating agent, feeding the mixture into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst to complete gas-phase carbonylation reaction, wherein the product after the reaction comprises dimethyl succinate. Common ethylene, carbon monoxide, methanol and oxygen are used as raw materials, and the raw materials are easy to obtain and have low price.
Description
Technical Field
The application relates to the technical field of fine chemical engineering, in particular to a method for synthesizing dimethyl succinate.
Background
Dimethyl succinate (English name: dimethyl succinate), also known as Dimethyl succinate, an organic compound of formula C 6 H 10 O 4 Molecular weight 146.14, colorless to pale yellow liquid (at room temperature), curable upon cooling. Slightly soluble in water and easily soluble in organic solvents such as diethyl ether, methanol, ethanol and acetone. The product can be widely used in the industries of food, spice, daily chemical industry, medicine, rubber, plastics, synthetic light stabilizer, high-grade paint, bactericide, medical intermediate and the like. The dimethyl succinate is used as an important chemical intermediate, and downstream products mainly comprise 1, 4-butanediol, tetrahydrofuran, gamma-butyrolactone, N-methyl pyrrolidone, mitiglinide, fumarate, dimethyl succinyl succinate, polybutylene succinate and the like.
Dimethyl succinate is mainly prepared by esterification reaction of raw materials of succinic acid and methanol under the catalytic action of concentrated sulfuric acid, p-toluenesulfonic acid or acidic resin serving as a catalyst. The process of catalyzing esterification by adopting concentrated sulfuric acid has the advantages of more side reactions, low yield, complex post-treatment, serious corrosion to equipment, and serious environmental pollution because the dimethyl sulfate byproduct is a toxic material. And the adoption of other catalysts generally causes the conditions of slow esterification reaction speed, difficult complete reaction and the like, and brings difficulty to subsequent separation and purification. The traditional route has no advantages from the economic perspective or the environmental protection perspective, and belongs to a process which is eliminated in the future.
The invention discloses a method for preparing dimethyl succinate and equipment thereof, which is characterized in that maleic anhydride and methanol are used as raw materials to prepare the dimethyl maleate, and then the dimethyl succinate is reacted with hydrogen to generate the dimethyl succinate under the action of a catalyst.
Chinese patent No. 102190582B discloses a method for simultaneously producing dimethyl succinate and 1, 4-butanediol, and specifically discloses a method for preparing dimethyl succinate from dimethyl maleate and hydrogen, which is similar to a maleic acid ester hydrogenation route developed by david corporation, and is a technical route with market competitiveness and development potential at present, but dimethyl maleate is generally prepared from maleic anhydride as a raw material, the maleic anhydride is from non-renewable fossil resources (C4 hydrocarbons or benzene is oxidized), the price influence of the fossil resources is large, and the whole process route is relatively limited by raw material sources and raw material costs. Therefore, the development of a new method for preparing dimethyl succinate by using a green and environment-friendly synthesis method with easily available raw materials and low cost has important significance and application background.
Disclosure of Invention
The application provides a method for synthesizing dimethyl succinate, which aims to solve the problems of limited sources of reaction raw materials and complicated steps in the prior art.
In order to solve the technical problem, the application provides a method for synthesizing dimethyl succinate, which comprises the following steps:
mixing a mixed gas containing inert gas, carbon monoxide, ethylene and methyl nitrite with a halogen-containing activating agent, feeding the mixture into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst to complete gas-phase carbonylation reaction, wherein the product after the reaction comprises dimethyl succinate.
Further, the temperature of the gas phase carbonylation reaction is 50.0-200.0 ℃, the reaction pressure is 0-1.0MPa (G), and the space velocity of the reaction volume is 100-10000h -1 。
Further, the volume concentration of each component of the mixed gas for completing the gas-phase carbonylation reaction is respectively as follows: the volume concentration of the ethylene is 1-80%, the volume concentration of the carbon monoxide is 5-80%, the volume concentration of the methyl nitrite is 5-50%, and the volume concentration of the inert gas is 1-80%.
Further, the inert gas is one or the combination of nitrogen, carbon dioxide and argon, a gas-phase product obtained by gas-liquid separation of reaction gas at the outlet of the reactor comprises nitric oxide generated by the reaction, the nitric oxide reacts with oxygen and methanol to regenerate methyl nitrite, an aqueous solution containing methanol and nitric acid components is discharged from the tower kettle of the methyl nitrite regeneration tower, and the methanol is recovered after the aqueous solution is treated.
Further, in the step of regenerating methyl nitrite, the gas circulation compressor is located before/after the methyl nitrite regenerating step equipment.
Further, the halogen-containing activating agent is one of methyl chloroformate, hydrogen chloride, phosgene, chlorine gas and halogenated nitroso or the combination thereof.
Further, the concentration of the halogen-containing activator in the fixed bed reactor inlet gas is 1-3000ppm.
Further, the additional position of the activator containing halogen is positioned at any position on the pipeline from the outlet of the methyl nitrite regenerating tower to the inlet of the carbonylation reactor.
Further, the heterogeneous catalyst is one or more palladium-containing compounds fixed on a carrier material, the carrier material is alumina, activated carbon, zeolite, aluminosilicate, metal phosphate or heteropoly acid, the palladium-containing compound is palladium chloride, palladium nitrate, palladium sulfate, palladium phosphate, palladium acetate, palladium oxalate or palladium benzoate, and the loading amount of palladium on the heterogeneous catalyst is 0.01-10%.
Further, a condenser is connected with a gas-liquid separator in series or a condenser is connected with a washing tower in series or a washing tower is connected with a condenser in series to obtain the gas product and the liquid product, and the temperature is controlled to be 0-50 ℃ after condensation.
The technical scheme at least comprises the following advantages:
(1) Common ethylene, carbon monoxide, methanol and oxygen are used as raw materials, and the raw materials are easy to obtain and have low price. At present, a large number of coal-to-olefin enterprises exist in China, and the method mainly comprises the steps of gasifying coal to generate carbon monoxide and hydrogen, then synthesizing the carbon monoxide and the hydrogen into methanol, and preparing olefin from the methanol. The route can be well suitable for enterprises of the type to produce the dimethyl succinate, replaces the original petroleum route to prepare the dimethyl succinate, and has good economic benefit and special strategic significance for China, such as countries rich in coal and oil;
(2) The reaction conditions are relatively mild, the reaction temperature and the reaction pressure are not too high, and the safety problem is avoided;
(3) The synthesis loop process flow is short, all reactions are continuously carried out in the carbonylation reactor and the esterification tower, the automatic control degree of the device is high, and the device can stably and continuously operate;
(4) The main product dimethyl succinate has larger boiling point difference with the byproducts dimethyl carbonate and dimethyl oxalate, is easy to separate, has low rectification cost and is easy to obtain high-quality products;
(5) The waste liquid generated in the production process is less, and the waste liquid can reach the standard and be discharged without special treatment;
(6) The heat generated by the reaction can generate low-pressure steam through the reaction steam drum, and is used for preheating the reaction gas, so that the energy self-supporting rate is high;
(7) The unreacted gas phase raw materials of ethylene and carbon monoxide are recycled, the unreacted liquid phase raw material of methanol is recycled, and the production process is green and environment-friendly.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic process flow diagram for preparing dimethyl succinate according to an embodiment of the present invention. Wherein, raw material gas carbon monoxide 1, raw material gas ethylene 2, raw material mixed gas 3, mixed gas 4 to be heated, preheated mixed gas 5, activating agent 6 containing halogen, carbonylation reactor inlet gas 7, carbonylation reactor outlet gas 8, cooling material 9 after reaction, detergent 10, liquid crude product 11 containing dimethyl succinate, recycle gas 12 after separating products, raw material gas oxygen 13, methyl nitrite regeneration tower inlet gas 14, aqueous solution 15 containing certain components such as methanol, nitric acid and the like, raw material methanol 16, synthesis cycle purge gas 17, recycle compressor inlet gas 18, carrier gas 19 and recycle compressor outlet gas 20;
a carbonylation reactor A, a condenser B, a product washing tower C, a methyl nitrite regeneration tower D, a gas circulating compressor E and a preheater F.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In addition, the technical features mentioned in the different embodiments of the present application described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for synthesizing dimethyl succinate, which comprises the following steps: mixing a mixed gas containing inert gas, carbon monoxide, ethylene and methyl nitrite with a halogen-containing activating agent, feeding the mixture into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst to finish gas-phase carbonylation reaction, wherein the product after the reaction comprises dimethyl succinate.
The method for synthesizing the dimethyl succinate specifically comprises the following steps:
step one, mixing a mixed gas containing inert gas, carbon monoxide, ethylene and methyl nitrite with a halogen-containing activating agent, feeding the mixed gas into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst to finish gas-phase carbonylation reaction, and performing gas-liquid separation on the reaction gas at the outlet of the reactor to obtain a liquid product containing dimethyl succinate;
and step two, gas which is discharged from the reactor after the reaction is separated to obtain a gas product and a liquid product. The gas product components are inert gas, unreacted carbon monoxide, ethylene and methyl nitrite, and nitrogen monoxide, nitrous oxide, methyl chloride and the like generated by reaction; the liquid product components comprise generated main products of dimethyl succinate, byproducts of dimethyl carbonate, dimethyl oxalate, methyl formate, methylal and the like;
thirdly, gas-phase products obtained after gas-liquid separation of reaction gas at the outlet of the reactor comprise inert gas, carbon monoxide, ethylene, methyl nitrite, nitric oxide, nitrous oxide, methyl chloride and the like, and the gas-phase products are sent to a methyl nitrite regeneration process to react nitric oxide, oxygen and methanol to regenerate methyl nitrite for recycling; in the gas circulation process, a small amount of gas is discharged out of the synthesis loop as purge gas, and the concentrations of inert gas in the circulation gas and gas impurities generated by reaction, such as nitrous oxide, methyl chloride and the like, are controlled within a reasonable range. Discharging aqueous solution containing certain components such as methanol, nitric acid and the like from the tower bottom of the methyl nitrite regeneration tower, and recovering the methanol after neutralization treatment, dehydration and separation of the aqueous solution.
In the first step, fresh feed gas of carbon monoxide and ethylene is mixed with the recycle gas, and the main components of the mixed recycle gas are inert gas, ethylene, carbon monoxide, methyl nitrite, nitric oxide and methanol, and a small amount of the inert gas, the ethylene, the carbon monoxide, the methyl nitrite, the nitric oxide and the methanolThe components are dinitrogen monoxide, chloromethane and the like. Heating the mixed gas to 60-120 ℃ by a steam heater, mixing the mixed gas with a halogen-containing activating agent, and feeding the mixed gas into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst for reaction, wherein the reaction temperature is 50.0-200.0 ℃, and preferably 100.0-150.0 ℃; the pressure of the reaction is 0 to 1.0MPa (G), preferably 0.1 to 0.6MPa (G); the reaction volume space velocity is 100-10000h -1 Preferably 1000-5000h -1 。
The ethylene volume concentration in the gas mixture at the reactor inlet is from 1 to 80%, preferably from 5 to 70%, particularly preferably from 30 to 60%; the volume concentration of carbon monoxide is 5-80%, preferably 8-40%, particularly preferably 10-30%; the methyl nitrite volume concentration is 5 to 50%, preferably 10 to 30%, particularly preferably 15 to 25%; the inert gas concentration is from 1 to 80% by volume, preferably from 5 to 60% by volume, particularly preferably from 10 to 30% by volume.
The inert gas can be one or more of nitrogen, carbon dioxide and argon, preferably nitrogen or/and carbon dioxide, and particularly preferably nitrogen.
The halogen-containing activating agent is selected from one or more of methyl chloroformate, hydrogen chloride, phosgene, chlorine gas and nitroso halide, preferably methyl chloroformate and hydrogen chloride, and particularly preferably hydrogen chloride. The concentration of the activating agent in the reactor inlet gas is from 1 to 3000ppm, preferably from 10 to 1000ppm by volume. The active agent supplement position can be located at any position on the pipeline from the outlet of the methyl nitrite regeneration tower to the inlet of the carbonylation reactor, and preferably is supplemented between the outlet of the preheater and the inlet of the reactor.
The catalyst is one or more palladium-containing compounds which have been fixed to a support material, where appropriate with the addition of a cocatalyst; the palladium compound may be selected from palladium chloride, palladium nitrate, palladium sulfate, palladium phosphate, palladium acetate, palladium oxalate and palladium benzoate, and the supported amount of palladium on the catalyst is 0.01 to 10%, preferably 0.1 to 5%, more preferably 0.2 to 2% (by weight). The carrier materials are alumina, activated carbon, zeolite, aluminosilicate, metal phosphate and heteropoly acid, preferably alumina and activated carbon, and particularly preferably alumina.
The gas-phase carbonylation reaction product is dimethyl succinate, and byproducts such as dimethyl carbonate, dimethyl oxalate, methyl formate, methylal and the like are generated at the same time. Catalyst is filled in the fixed bed reactor tubes, water is adopted outside the tubes to generate steam to remove reaction heat, and the generated steam can be used for preheating reaction gas.
The relevant reactions are as follows:
carbonylation of ethylene, carbon monoxide and methyl nitrite to dimethyl succinate over palladium catalyst
Side reaction for generating dimethyl carbonate:
side reaction for generating dimethyl oxalate:
side reaction to form methyl formate:
2CH 3 ONO→HCOOCH 3 +N 2 O+H 2 O
side reactions to form methylal:
2CH 3 ONO+CH 3 OH→CH 3 OCH 2 OCH 3 +2NO+H 2 O
in the second step, the gas discharged from the reactor after the reaction is separated to obtain a gas product and a liquid product. The gas product components are inert gas, unreacted carbon monoxide, ethylene and methyl nitrite, and nitrogen monoxide, nitrous oxide, methyl chloride and the like generated by reaction; the liquid product components comprise generated main products of dimethyl succinate, byproducts of dimethyl carbonate, dimethyl oxalate, methyl formate, methylal and the like.
And separating to obtain gas-phase products and liquid-phase products in a mode that a condenser is connected with a gas-liquid separator in series or the condenser is connected with a washing tower in series or the washing tower is connected with the condenser in series. The temperature after condensation in the condenser is controlled to be 0-50 ℃, preferably 35-45 ℃. The washing tower uses methanol as detergent, methanol is added from the top of the tower, dimethyl oxalate can be added as second detergent, and dimethyl oxalate is added from the tower.
In the third step, the gas product containing inert gas, carbon monoxide, ethylene, methyl nitrite, nitric oxide, nitrous oxide, methyl chloride and other components is sent to a methyl nitrite regeneration process, nitric oxide and oxygen are mixed and react with methanol in a methyl nitrite regeneration tower to regenerate methyl nitrite, and the regenerated gas is recycled after being washed and dehydrated by methanol.
The reaction of nitric oxide, oxygen and methanol to regenerate methyl nitrite is as follows:
in the gas circulation process, a small amount of gas is discharged out of the synthesis loop as purge gas, and the concentrations of inert gas in the circulation gas and gas impurities generated by reaction, such as nitrous oxide, methyl chloride and the like, are controlled within a reasonable range. Discharging aqueous solution containing certain components such as methanol, nitric acid and the like from the tower bottom of the methyl nitrite regeneration tower, and recovering the methanol after neutralization treatment, dehydration and separation of the aqueous solution.
In order to maintain the nitrogen balance of the system, a certain amount of nitric oxide or other nitrogen oxides may be supplemented to the methyl nitrite regeneration step, or a certain amount of nitric acid may be supplemented to the methyl nitrite regeneration tower.
In the gas circulation, the position of the gas circulation compressor may be located before/after the methyl nitrite regenerating process, and the position of the purge gas may be located before/after the methyl nitrite regenerating process.
Fig. 1 is a schematic process flow diagram for preparing dimethyl succinate according to an embodiment of the present invention. Referring to fig. 1, raw material gas carbon monoxide 1 and raw material gas ethylene 2 are mixed to form raw material mixed gas 3, the mixed gas 3 and recycle compressor outlet gas 20 are mixed to form mixed gas 4 to be heated and enter a preheater F, preheated mixed gas 5 from the preheater F is mixed with a halogen-containing activating agent 6 and enters a carbonylation reactor a as carbonylation reactor inlet gas 7 to carry out carbonylation reaction, carbonylation reactor outlet gas 8 from the carbonylation reactor a passes through a condenser B to form a reaction cooling material 9, then enters a product washing tower C, a liquid crude product 11 containing dimethyl succinate and a product-separated recycle gas 12 are obtained after being treated by a washing agent 10, the product-separated recycle gas 12 and raw material gas oxygen 13 enter a methyl nitrite regeneration tower D as methyl nitrite regeneration tower inlet gas 14, raw material methanol 16 is added to react and regenerate methyl nitrite, and an aqueous solution 15 containing certain components such as methanol, nitric acid and the like is discharged from a methyl nitrite regeneration tower. In the gas circulation process, the synthesis loop purge gas 17 is discharged from the synthesis loop as purge gas to control the concentration of inert gas in the circulation gas and gas impurities generated by reaction, such as nitrous oxide, methyl chloride and the like, within a reasonable range. The inlet gas 18 of the circulating compressor enters the gas circulating compressor E, the carrier gas 19 is added, and the outlet gas 20 of the circulating compressor is added into the mixed gas 3 to be used as the formed gas in the mixed gas 4 to be heated for recycling.
Example 1
50kg of PdCl having a palladium content of 1.6% 2 the/C catalyst is filled into a carbonylation reactor, the inner diameter of the tube array of the carbonylation reactor is 30mm, the distance between the tube arrays is 45mm, the length of the tube array is 4.0 meters, and 40 tube arrays are arranged in the tube array.
220Nm 3 The recycle gas/h (containing 10% methyl nitrite, 12% carbon monoxide, 30% ethylene, 10% methanol, 4% nitric oxide, 7% carbon dioxide, 24% nitrogen, 0.8% nitrous oxide, 0.4% methyl chloride, and 1.8% of other impurity gases) was heated to 100.0 ℃ by a steam preheater, mixed with 30NL/h HCl, and fed into the carbonylation reactor to react. Under the conditions of the reaction temperature of 110.0 ℃ and the reaction pressure of 0.1MPa (G), ethylene, carbon monoxide and methyl nitrite react to generate dimethyl succinate.
And cooling the gas product after reaction to 38.0 ℃ through a condenser, and then introducing the gas product into a product washing tower for gas-liquid separation after methanol washing. The liquid product flow was 28.22kg/h, the analytical composition was: 8.32 percent of methanol and succinic acid86.43% of dimethyl ester, 1.88% of dimethyl carbonate, 0.36% of dimethyl oxalate, 0.18% of methyl formate, 0.49% of methylal and the like. The results show that the space-time yield of dimethyl succinate is: 243.90kg/m 3 cat.h。
Product scrubber outlet gas and 2.01Nm 3 Mixing oxygen and entering the bottom of a methyl nitrite regeneration tower. 24.0kg/h of methanol is added into the top of a methyl nitrite regeneration tower, 15.4kg/h of methanol aqueous solution containing 20.58% of water is discharged from the tower bottom, the solution contains nitric acid with the concentration of less than 1%, and the methanol is recovered after the solution is subjected to alkali treatment and dehydration treatment. Most of the methyl nitrite regeneration tower top gas is sent to a circulating compressor, and a small amount of gas is used as purge gas to control the concentration of impurity gases such as nitrous oxide, methyl chloride and the like within a reasonable range.
And a certain amount of nitrogen is supplemented to the working section of the circulating compressor to be used as dry gas seal, and a certain amount of nitrogen is also supplemented to any position of the circulating pipeline of the synthetic ring to keep the concentration of the inert gas of the synthetic ring within a reasonable range.
Pressurized recycle gas make-up of 8.03Nm 3 Carbon monoxide,/h and 3.81Nm 3 The/h ethylene enters the steam preheater.
Example 2
60kg of PdCl having a palladium content of 1.0% 2 /Al 2 O 3 The catalyst is filled into a carbonylation reactor, the inner diameter of the tube array of the carbonylation reactor is 30mm, the distance between the tube arrays is 45mm, the length of the tube array is 4.0 meters, and 40 tube arrays are arranged in the tube array.
300Nm 3 The recycle gas/h (consisting of 15% methyl nitrite, 10% carbon monoxide, 40% ethylene, 5% methanol, 4% nitric oxide, 5% carbon dioxide, 18% nitrogen, 0.7% nitrous oxide, 0.2% methyl chloride, and 2.1% of other impurity gases) was heated to 110.0 ℃ by a steam preheater, mixed with 20NL/h HCl and fed into the carbonylation reactor for reaction. Under the conditions of the reaction temperature of 125.0 ℃ and the reaction pressure of 0.2MPa (G), ethylene, carbon monoxide and methyl nitrite react to generate dimethyl succinate.
Cooling the reacted gas product to 40.0 deg.c in a condenser, and washing in a product washing towerAnd carrying out gas-liquid separation after alcohol washing. The liquid product flow was 36.0kg/h, the analytical composition was: 5.62 percent of methanol, 88.23 percent of succinic acid dimethyl ester, 2.36 percent of carbonic acid dimethyl ester, 0.84 percent of oxalic acid dimethyl ester, 0.21 percent of methyl formate, 0.63 percent of methylal and the like. The results show that the space-time yield of dimethyl succinate is: 317.63kg/m 3 cat.h。
Product scrubber outlet gas and 2.65Nm 3 Mixing oxygen and entering the bottom of a methyl nitrite regeneration tower. 30kg/h of methanol was fed to the top of the methyl nitrite regeneration column, and 19.6kg/h of an aqueous 21.4% aqueous methanol solution was discharged from the bottom of the column. The methanol aqueous solution treatment, purge gas discharge control, and cyclic compression section operation were the same as in example 1. Pressurized recycle gas make-up of 10.60Nm 3 Carbon monoxide per hour and 4.97Nm 3 The/h ethylene enters the steam preheater.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of this invention are intended to be covered by the scope of the invention as expressed herein.
Claims (10)
1. A synthetic method of dimethyl succinate is characterized by comprising the following steps:
mixing a mixed gas containing inert gas, carbon monoxide, ethylene and methyl nitrite with a halogen-containing activating agent, feeding the mixture into a fixed bed reactor filled with a platinum group metal heterogeneous catalyst to complete gas-phase carbonylation reaction, wherein the product after the reaction comprises dimethyl succinate.
2. The method for synthesizing dimethyl succinate according to claim 1, wherein the temperature of the gas phase carbonylation is 50.0-200.0 ℃, the reaction pressure is 0-1.0MPa (G), and the space velocity of the reaction volume is 100-10000h -1 。
3. The method for synthesizing dimethyl succinate according to claim 1, wherein the volume concentration of each component of the mixed gas for completing the gas-phase carbonylation reaction is respectively as follows: the volume concentration of the ethylene is 1-80%, the volume concentration of the carbon monoxide is 5-80%, the volume concentration of the methyl nitrite is 5-50%, and the volume concentration of the inert gas is 1-80%.
4. The method for synthesizing dimethyl succinate as claimed in claim 1, wherein the inert gas is one or the combination of nitrogen, carbon dioxide and argon, the gas-phase product obtained by gas-liquid separation of the reaction gas at the outlet of the reactor contains nitrogen monoxide generated by the reaction, the nitrogen monoxide reacts with oxygen and methanol to regenerate methyl nitrite, the tower bottom of the methyl nitrite regeneration tower discharges the aqueous solution containing methanol and nitric acid components, and the aqueous solution is treated to recover methanol.
5. The method for synthesizing dimethyl succinate according to claim 4, wherein the gas recycle compressor is located before/after the methyl nitrite regeneration process equipment in the process of producing methyl nitrite.
6. The method for synthesizing dimethyl succinate according to claim 1, wherein the halogen-containing activating agent is one or the combination of methyl chloroformate, hydrogen chloride, phosgene, chlorine and halogenated nitroso.
7. The method for synthesizing dimethyl succinate according to claim 1, wherein the concentration of the halogen-containing activating agent in the inlet gas of the fixed bed reactor is 1-3000ppm.
8. The method for synthesizing the dimethyl succinate according to claim 1, wherein the halogen-containing activator is supplemented at any position on a pipeline from an outlet of the methyl nitrite regeneration tower to an inlet of the carbonylation reactor.
9. The method of claim 1, wherein the heterogeneous catalyst comprises one or more palladium-containing compounds immobilized on a carrier material, the carrier material is selected from the group consisting of alumina, activated carbon, zeolites, aluminosilicates, metal phosphates, and heteropoly acids, the palladium-containing compound is selected from the group consisting of palladium chloride, palladium nitrate, palladium sulfate, palladium phosphate, palladium acetate, palladium oxalate, and palladium benzoate, and the loading of palladium on the heterogeneous catalyst is 0.01-10%.
10. The method for synthesizing dimethyl succinate according to claim 1, wherein the gas product and the liquid product are obtained by connecting a condenser in series with a gas-liquid separator or a condenser in series with a washing tower or a washing tower in series with a condenser, and the temperature after condensation is controlled to be 0-50 ℃.
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