CN105330542A - Production method of dimethyl oxalate - Google Patents

Production method of dimethyl oxalate Download PDF

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Publication number
CN105330542A
CN105330542A CN201410314462.0A CN201410314462A CN105330542A CN 105330542 A CN105330542 A CN 105330542A CN 201410314462 A CN201410314462 A CN 201410314462A CN 105330542 A CN105330542 A CN 105330542A
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China
Prior art keywords
dimethyl oxalate
tower
production method
recovery tower
reactor
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CN201410314462.0A
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Inventor
杨卫胜
贺来宾
施德
胡松
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to CN201410314462.0A priority Critical patent/CN105330542A/en
Priority to AU2015203732A priority patent/AU2015203732B2/en
Priority to BR102015016125A priority patent/BR102015016125B8/en
Priority to CA2896290A priority patent/CA2896290C/en
Priority to RU2015126664A priority patent/RU2692099C2/en
Publication of CN105330542A publication Critical patent/CN105330542A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • 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 relates to a production method of dimethyl oxalate, and mainly solves the problems of complex process, plugging of equipment and piping by dimethyl oxalate, and high material consumption and energy consumption in the prior art. The method comprises the following steps: a) carrying out contact reaction on gas containing CO and methyl nitrite with a platinum metal catalyst in a coupling reactor to obtain a material flow containing dimethyl oxalate; b) directly sending the material flow containing dimethyl oxalate without cooling into a dimethyl oxalate recovery tower, sending a material flow containing methanol from the top of the dimethyl oxalate recovery tower to conduct countercurrent contact with the material flow containing dimethyl oxalate; and collecting crude methanol and non-condensable gas from the tower top, and collecting the dimethyl oxalate product at tower bottom. The technical scheme can better solve the problems and can be used in the industrial production of dimethyl oxalate.

Description

The production method of dimethyl oxalate
Technical field
The present invention relates to a kind of production method of dimethyl oxalate, specifically, take coal based synthetic gas as the method for raw material production dimethyl oxalate.
Background technology
Dimethyl oxalate (DMO), as important intermediates, can be hydrolyzed oxalic acid processed, also can Hydrogenation ethylene glycol, has important purposes in chemical industry.The synthetic route of DMO mainly contains two: Article 1 route generates by methyl alcohol and oxalic acid esterification, there is waste discharge amount large, the shortcoming that environmental pollution is serious; Another route is that linked reaction under palladium system or platinum group catalyst generates by CO and methyl nitrite.Because Developing Coal Chemical Industry is in recent years rapid, Article 2 route to cause through the intermediate steps of synthetic gas preparing ethylene glycol as coal and pays close attention to widely, and CO is at loading type Pd/α-Al 2o 3under catalyst action, generate DMO and NO with methyl nitrite linked reaction under normal pressure, main reaction equation is as follows:
2CO+2CH 3ONO→(COOCH 3) 2+2NO
Side reaction mainly contains CO and methyl nitrite and reacts and generate NO and methylcarbonate, and methyl nitrite decomposes and generates NO, methyl-formiate and methyl alcohol, CO and NO reaction generation N 2and CO 2, chemical equation is as follows:
CO+2CH 3ONO→2NO+C 3H 6O 3
4CH 3ONO→4NO+C 2H 4O 2+2CH 3OH
2CO+2NO→N 2+2CO 2
At present, in existing technique, generally first adopt methanol absorption, after methyl alcohol, methylcarbonate being separated with DMO, then adopt the technique of membrane sepn or variable-pressure rectification or separation of extractive distillation methyl alcohol and methylcarbonate to obtain pure DMO product.The pure DMO product obtained can directly as product or the raw material as synthesizing glycol.Namely purification DMO need come through the technique of alcohol washing tower, alcohol recovery tower and rectifying tower.
The patent US4453026A of Ube company discloses and CO and nitrous acid (first or second) ester is reacted under platinum group noble metal catalyst, and reaction product is carried out condensation, is separated and obtains phlegma and non-condensable gas.Add a certain amount of methyl alcohol in the process of condensation, avoid oxalic acid two (first or second) ester to be mixed into non-condensable gas and crystallization.Phlegma enters elementary rectifying tower, obtains thick oxalic acid two (first or second) ester product.
In document CN101993367A, CN101993365A, CN101993369A, CN101993361A, CN101492370A and CN101381309A, the reaction product of CO and nitrous acid ester will obtain gas phase overhead product and liquid phase overhead product through gas-liquid separation, then the liquid phase distillate containing barkite is carried out separating-purifying again and obtains thick product.Scrubber tower is separated DMO with the flow process of DMO rectifying tower to adopt primary flash to add in document CN202643601U, because scrubber tower low-temperature methanol is washed, causes dimethyl oxalate at crystallization inside tower.
Disclose CO and methyl nitrite contact with platinum group noble metal catalyst in document CN101462961A and react, obtain the product of DMO and methylcarbonate.Product is entered in condenser and carry out contacting with methyl alcohol and condensation, obtain non-condensable gas and phlegma, containing DMO, methylcarbonate, methyl-formiate and methyl alcohol in phlegma.Phlegma is entered distillation tower distill, tower top obtains the azeotrope of methylcarbonate and methyl alcohol, and tower reactor obtains the material containing DMO.The method flow process is complicated, and has relatively high condensation point due to dimethyl oxalate, can crystallize out, finally block condenser in condenser wall.
In a word, in prior art, coupled product all first enters down-stream again through cooling, and technical process is complicated; Dimethyl oxalate is easy crystallization in e-quipment and pipe, and for preventing occluding device and pipeline, need be incubated or accompany heat, energy consumption is high; Meanwhile, the yield of dimethyl oxalate is also have impact at e-quipment and pipe intercrystalline.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists technical process complexity, dimethyl oxalate occluding device and pipeline, and material consumption and the high problem of energy consumption, provide a kind of production method of new dimethyl oxalate.It is simple that the method has technical process, and energy consumption is low, the feature that dimethyl oxalate yield is high.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of production method of dimethyl oxalate, comprises the following steps:
A) to contact with platinum group metal catalysts in coupler reactor with the gas of methyl nitrite containing CO and react, obtain the logistics containing dimethyl oxalate;
B) the described logistics containing dimethyl oxalate does not cool and directly enters dimethyl oxalate recovery tower, the logistics comprising methyl alcohol enters and the described logistics counter current contact containing dimethyl oxalate from dimethyl oxalate recovery tower tower top, tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product.
In technique scheme, preferably, described comprise methyl alcohol logistics charging place and described logistics charging place containing dimethyl oxalate between for load Packed absorption distillation section, described containing between logistics charging place of dimethyl oxalate and tower reactor is the stripping section adopting valve tray.
In technique scheme, preferably, the aspect ratio of described absorption distillation section and stripping section is 0.5 ~ 5.More preferably, the aspect ratio of described absorption distillation section and stripping section is 1 ~ 2.
In technique scheme, preferably, dimethyl oxalate recovery tower stripping section theoretical plate number is 5 ~ 40 pieces.
In technique scheme, preferably, dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, and working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG.
In technique scheme, preferably, the operational condition of described coupler reactor is: temperature of reaction 50 ~ 200 DEG C, pressure 0 ~ 1MPa.
In technique scheme, preferably, the pipeline between coupler reactor and dimethyl oxalate recovery tower adopts low-pressure steam to accompany heat.
In technique scheme, preferably, dimethyl oxalate recovery tower tower reactor discharge pipe adopts low-pressure steam companion heat.
In technique scheme, preferably, described filler is regular or dumped packing, and described column plate is valve tray, sieve plate, double pass tray, bubble cap plate or Thorman tray.
In the inventive method, the first step is CO linked reaction synthesizing dimethyl oxalate.Gas raw material containing CO and methyl nitrite enters into the reactor being filled with solid platinum catalyzer and carries out gas phase catalytic reaction.Coupler reactor is calandria type fixed bed reactor, and reactor adopts circulating hot water to remove heat and byproduct steam.The residence time of vapor-phase reactant in beds is no more than at most 12 seconds, and the suitable residence time is 0.2 ~ 6 second.Before entering the reactor, usual rare gas element is as nitrogen or CO for gas reaction raw material 2dilution.Reaction can be carried out at relatively low temperature, and typical temperature is 50 ~ 200 DEG C, and preferable temperature is 60 ~ 180 DEG C.For reaction pressure, can be 0 ~ 2MPa, be preferably 0 ~ 1MPa.In gas phase initial feed, the concentration of methyl nitrite can have a greater change scope, but in order to obtain suitable speed of reaction, the concentration of methyl nitrite is minimum must not lower than the volumetric concentration of 3%, preferably 5 ~ 30% volumetric concentrations.In gas phase initial feed, the concentration of CO also can have a greater change scope, and general control is in 10 ~ 90% volumetric concentrations.
In the inventive method, second step is the separation of dimethyl oxalate.Coupler reactor outlet reaction product does not cool and directly enters in the middle part of dimethyl oxalate recovery tower, and methyl alcohol enters and linked reaction product counter current contact from tower top, and tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product.Between methanol feeding and the charging of linked reaction product, part is absorber portion, adopt the regular or dumped packing of efficient low-resistance, absorber portion plays rectifying section effect simultaneously, be stripping section containing logistics charging place of dimethyl oxalate to tower reactor part, adopt valve tray, sieve plate, double pass tray, bubble cap plate or Thorman tray.Dimethyl oxalate recovery tower overhead gas is through condensation, and non-condensable gas part goes subsequent disposal, and a liquid phase part send subsequent disposal as the extraction of crude carbinol product, and another part mixes with methanol feeding and refluxes as dimethyl oxalate recovery tower.Coupler reactor outlet enters dimethyl oxalate recovery tower pipeline and dimethyl oxalate recovery tower tower reactor discharge pipe all adopts low-pressure steam to accompany heat, prevents dimethyl oxalate crystallization in rectifying tower e-quipment and pipe.Dimethyl oxalate recovery tower stripping section theoretical plate number is 5 ~ 40 pieces.Dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, and working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG.
Adopt the inventive method, the absorption of coupled product in prior art in cooling apparatus and two unit operations of the rectifying in distillation plant are focused in a dimethyl oxalate recovery tower and completes, and coupled product does not cool and directly enters dimethyl oxalate recovery tower, makes energy consumption reduce; Prevent dimethyl oxalate crystallization in cooling apparatus, improve the yield of dimethyl oxalate; Save facility investment and floor space; Meanwhile, the simplification of flow process also makes insulation accompany the expense of heat to greatly reduce.In a word, adopt the inventive method, dimethyl oxalate yield can reach 99.5% and more than, barkite recovery system energy consumption 60% can be reduced, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic diagram.
In Fig. 1, R-101 is coupler reactor, C-101 is dimethyl oxalate recovery tower, D-102 is DMO recovery tower return tank, 1 is nitrogen feed, 2 is CO charging, and 3 is methanol feeding, and 4 is methyl nitrite charging, 5 is reactor feed, 6 is reactor discharging, and 7 is absorption agent methanol feeding, and 8 is dimethyl oxalate recovery tower overhead gas, 9 is dimethyl oxalate recovery tower non-condensable gas, 10 dimethyl oxalate recovery tower phegmas, 11 crude carbinol products, 12 is dimethyl oxalate recovery tower tower bottoms (dimethyl oxalate product).
In Fig. 1, nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 enter coupler reactor R-101 after mixing after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101, absorption agent methyl alcohol 7 mixes with dimethyl oxalate recovery tower phegma and enters from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate product 12 is from tower reactor extraction.Wherein, logistics 6 and logistics 12 pipeline accompany heat by low-pressure steam, prevent dimethyl oxalate crystallization in rectifying tower e-quipment and pipe.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 mix after totally 30 tons/hour, coupler reactor R-101 is entered after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101,20 tons of/hour methyl alcohol 7 mix with dimethyl oxalate recovery tower phegma and enter from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate product 12 is from tower reactor extraction.Dimethyl oxalate yield is 100%.
Dimethyl oxalate recovery tower dumped packing height is 10 meters, and stripping section theoretical plate number is 10 pieces, and the aspect ratio of absorption distillation section and stripping section is 2; Tower top service temperature is 32 DEG C, and working pressure is 40kPaG; Tower reactor service temperature is 185 DEG C, and working pressure is 85kPaG, reboiler heat duty 4.0435MW.
Wherein, reactor feed and main streams composed as follows:
Logistics 5 6 7 9 11 12
Temperature, DEG C 110 120 40 20 20 185
Pressure, kPaG 230 110 850 40 40 85
Weight forms, %
N 2 44.30 44.30 0 50.15 180ppm 0
CO 19.08 10.17 0 11.51 171ppm 0
NO 5.23 15.07 0 17.06 134ppm 0
CO 2 0 30ppm 0 34ppm 307ppm 0
Methyl nitrite 29.74 9.72 0 11.01 1.03 0
Methyl-formiate 0 0 0 0 346ppm 0
Methyl alcohol 1.65 1.7 99.78 9.59 94.40 0
Methylcarbonate 0 0.57 0.217 0.627 4.48 0.144
Water 0 0 50ppm 0 14.7ppm 16ppm
Dimethyl oxalate 0 18.41 0 0 0 99.85
[embodiment 2]
Identical with [embodiment 1] embodiment, unlike the device parameter of feed composition and tower.
Dimethyl oxalate recovery tower dumped packing height is 15 meters, and stripping section theoretical plate number is 20 pieces, and the aspect ratio of absorption distillation section and stripping section is 1.5; Tower top service temperature is 29 DEG C, and working pressure is 20kPaG; Tower reactor service temperature is 178 DEG C, and working pressure is 50kPaG, reboiler heat duty 3.680MW.Dimethyl oxalate yield is 100%.
Wherein, reactor feed and main streams composed as follows:
Logistics 5 6 7 9 11 12
Temperature, DEG C 110 120 40 15 15 178
Pressure, kPaG 210 110 850 10 10 50
Weight forms, %
N 2 44.30 44.30 0 140ppm 50.63 0
CO 15.61 6.59 0 90ppm 7.53 0
NO 8.71 18.79 0 150ppm 21.47 0
CO 2 0 50ppm 0 0 60ppm 0
Methyl nitrite 29.74 9.22 0 0.88 10.52 0
Methyl-formiate 0 730ppm 0 490ppm 830ppm 0
Methyl alcohol 1.65 1.72 99.77 91.96 8.85 0
Methylcarbonate 0 0.88 0.22 7.07 0.89 0.14
Water 0 0 50ppm 10ppm 0 20ppm
Dimethyl oxalate 0 18.41 0 0 0 ＞99.85
[embodiment 3]
Identical with [embodiment 1] embodiment, unlike the device parameter of feed composition and tower.
Dimethyl oxalate recovery tower dumped packing height is 20 meters, and stripping section theoretical plate number is 30 pieces, and the aspect ratio of absorption distillation section and stripping section is 1.35; Tower top service temperature is 34 DEG C, and working pressure is 60kPaG; Tower reactor service temperature is 187 DEG C, and working pressure is 100kPaG, reboiler heat duty 4.801MW.Dimethyl oxalate yield is 100%.
Wherein, reactor feed and main streams composed as follows:
Logistics 5 6 7 9 11 12
Temperature, DEG C 110 110 40 15 15 189
Pressure, kPaG 210 110 850 40 40 100
Weight forms, %
N 2 46.86 46.87 0 190ppm 53.42 0
CO 17.51 9.42 0 160ppm 10.74 0
NO 9.35 18.38 0 180ppm 20.95 0
CO 2 0 50ppm 0 0 6ppm 0
Methyl nitrite 24.49 6.12 0 0.72 6.96 0
Methyl-formiate 0 600ppm 0 490ppm 680ppm 0
Methyl alcohol 1.77 1.83 99.77 92.58 7.17 0
Methylcarbonate 0 0.72 0.22 6.58 0.67 0.14
Water 0 0 50ppm 10ppm 0 20ppm
Dimethyl oxalate 0 16.58 0 0 0 ＞99.85
[embodiment 4]
Identical with [embodiment 1] embodiment, unlike the device parameter of feed composition and tower.
The structured packing of dimethyl oxalate recovery tower is highly 25 meters, and stripping section theoretical plate number is 40 pieces, and the aspect ratio of absorption distillation section and stripping section is 1.25; Tower top service temperature is 36 DEG C, and working pressure is 80kPaG; Tower reactor service temperature is 192 DEG C, and working pressure is 120kPaG, reboiler heat duty 4.769MW.Dimethyl oxalate yield is 100%.
Wherein, reactor feed and main streams composed as follows:
Logistics 5 6 7 9 11 12
Temperature, DEG C 110 110 40 15 15 192
Pressure, kPaG 210 110 850 60 60 120
Weight forms, %
N 2 46.86 46.86 0 220ppm 53.97 0
CO 17.52 9.42 0 190ppm 10.85 0
NO 9.35 18.38 0 200ppm 21.17 0
CO 2 0 50ppm 0 0 60ppm 0
Methyl nitrite 24.49 6.12 0 0.83 7.03 0
Methyl-formiate 0 600ppm 0 560ppm 0.07 0
Methyl alcohol 1.77 1.83 99.78 92.03 6.27 0
Methylcarbonate 0 0.72 0.22 7.02 0.63 0.14
Water 0 0 50ppm 10ppm 0 20ppm
Dimethyl oxalate 0 16.59 0 0 0 ＞99.85
[comparative example 1]
The reaction conditions identical with [embodiment 4], utilizes device disclosed in document CN202643601U, and linked reaction product is first through interchanger cooling, and a part of dimethyl oxalate is condensed; Gas phase in interchanger and liquid phase all enter gas-liquid separator, obtain the dimethyl oxalate that can directly utilize bottom gas-liquid separator; Remaining dimethyl oxalate goes to absorption tower to utilize methanol absorption in uncondensable gas phase, finally absorption liquid fractionation by distillation is obtained dimethyl oxalate.
Wherein, gas-liquid mixture is cooled to 60 ~ 70 DEG C in interchanger, absorption tower packed height is 25 meters, total absorption methanol usage adopts [embodiment 4] dimethyl oxalate in preparation recovery tower top always to absorb quantity of methyl alcohol, dimethyl oxalate rectifying tower 40 blocks of theoretical trays, the reboiler needed is 11.849MW, and energy consumption is significantly higher than [embodiment 4] reboiler heat duty 4.769MW.Further, in device disclosed in document CN202643601U, dimethyl oxalate is had to crystallize out in the pipeline on interchanger, absorption tower wall, between interchanger to dimethyl oxalate rectifying tower, occluding device and pipeline.

Claims (10)

1. a production method for dimethyl oxalate, comprises the following steps:
A) to contact with platinum group metal catalysts in coupler reactor with the gas of methyl nitrite containing CO and react, obtain the logistics containing dimethyl oxalate;
B) the described logistics containing dimethyl oxalate does not cool and directly enters dimethyl oxalate recovery tower, the logistics comprising methyl alcohol enters and the described logistics counter current contact containing dimethyl oxalate from dimethyl oxalate recovery tower tower top, tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product.
2. the production method of dimethyl oxalate according to claim 1, it is characterized in that in described dimethyl oxalate recovery tower, described comprise methyl alcohol logistics charging place and described logistics charging place containing dimethyl oxalate between for load Packed absorption distillation section, described containing between logistics charging place of dimethyl oxalate and tower reactor is the stripping section adopting column plate.
3. the production method of dimethyl oxalate according to claim 2, is characterized in that the aspect ratio of described absorption distillation section and stripping section is 0.5 ~ 5.
4. the production method of dimethyl oxalate according to claim 3, is characterized in that the aspect ratio of described absorption distillation section and stripping section is 1 ~ 2.
5. the production method of dimethyl oxalate according to claim 2, is characterized in that dimethyl oxalate recovery tower stripping section theoretical plate number is 5 ~ 40 pieces.
6. the production method of dimethyl oxalate according to claim 2, it is characterized in that described filler is regular or dumped packing, described column plate is valve tray, sieve plate, double pass tray, bubble cap plate or Thorman tray.
7. the production method of dimethyl oxalate according to claim 1, it is characterized in that dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG.
8. the production method of dimethyl oxalate according to claim 1, is characterized in that the operational condition of described coupler reactor is: temperature of reaction 50 ~ 200 DEG C, pressure 0 ~ 1.0MPa.
9. the production method of dimethyl oxalate according to claim 1, is characterized in that the pipeline between coupler reactor and dimethyl oxalate recovery tower adopts low-pressure steam to accompany heat.
10. the production method of dimethyl oxalate according to claim 1, is characterized in that dimethyl oxalate recovery tower tower reactor discharge pipe adopts low-pressure steam companion heat.
CN201410314462.0A 2014-07-03 2014-07-03 Production method of dimethyl oxalate Pending CN105330542A (en)

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CN201410314462.0A CN105330542A (en) 2014-07-03 2014-07-03 Production method of dimethyl oxalate
AU2015203732A AU2015203732B2 (en) 2014-07-03 2015-07-03 Method for producing dimethyl oxalate
BR102015016125A BR102015016125B8 (en) 2014-07-03 2015-07-03 method for producing dimethyl oxalate and method for producing dimethyl oxalate and dimethyl carbonate as a by-product
CA2896290A CA2896290C (en) 2014-07-03 2015-07-03 Method for producing dimethyl oxalate
RU2015126664A RU2692099C2 (en) 2014-07-03 2015-07-03 Dimethyl oxalate production method

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CN112174821A (en) * 2020-09-04 2021-01-05 中盐安徽红四方股份有限公司 Rectification method of dimethyl oxalate

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CN106693431A (en) * 2017-03-17 2017-05-24 河南中托力合化学有限公司 Novel heptane precise fractionation device
CN109096049A (en) * 2018-07-03 2018-12-28 沈阳化工大学 A kind of method that esterification eliminates dimethyl ester mesoxalic acid and obtains polyester grade ethylene glycol
CN112174821A (en) * 2020-09-04 2021-01-05 中盐安徽红四方股份有限公司 Rectification method of dimethyl oxalate
CN112174821B (en) * 2020-09-04 2023-08-18 中盐安徽红四方股份有限公司 Rectification method of dimethyl oxalate

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AU2015203732A1 (en) 2016-01-21
RU2692099C2 (en) 2019-06-21
RU2015126664A3 (en) 2019-01-31
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BR102015016125B8 (en) 2021-05-18
BR102015016125A2 (en) 2018-06-12

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