CN104262152A - Production method of methyl glycolate - Google Patents
Production method of methyl glycolate Download PDFInfo
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- CN104262152A CN104262152A CN201410471390.0A CN201410471390A CN104262152A CN 104262152 A CN104262152 A CN 104262152A CN 201410471390 A CN201410471390 A CN 201410471390A CN 104262152 A CN104262152 A CN 104262152A
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- methyl glycolate
- dimethyl oxalate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention relates to a production method of methyl glycolate, aiming to mainly solve the problems of low conversion rate of dimethyl oxalate and low selectivity of methyl glycolate in the prior art. The production method of methyl glycolate comprises the following steps of (1) enabling a mixed material composed of a methanol solution of dimethyl oxalate and feed gas containing hydrogen to be in contact with a silver-containing catalyst in a reactor to react to obtain a mixture flow containing methyl glycolate, carrying out heat exchange, and then, enabling the mixture flow to enter a gas-liquid separation system; (2) sequentially carrying out condensation, primary gas-liquid separation, condensation and secondary low-temperature gas-liquid separation on the mixture flow subjected to heat exchange to obtain crude methyl glycolate; and (3) carrying out reduced-pressure distillation separation on crude methyl glycolate to obtain the methyl glycolate product. According to the technical scheme, the conversion rate of dimethyl oxalate can be higher than 99%, the selectivity of methyl glycolate can be higher than 80%, and the production method can be applied to industrial production of methyl glycolate.
Description
Technical field
The present invention relates to a kind of method of producing methyl glycolate.
Background technology
Methyl glycolate (HOCH
2cOOCH
3, MG) and be a kind of important Chemicals and intermediate, because it has hydroxyl and ester functional groups simultaneously, make it have the chemical property of alcohol and ester concurrently, be widely used in many fields such as chemical industry, medicine, agricultural chemicals, feed, dyestuff and spices.Mainly comprise: 1) as the fine solvent in fiber, resin, rubber, semi-conductor; 2) further hydrogenating reduction preparing ethylene glycol; 3) carbonylation propanedioic acid (list) methyl esters; 4) ammonia solution glycine; 5) oxydehydrogenation glyoxalic acid methylester; 6) oxyacetic acid processed etc. is hydrolyzed.In all multi-usages of methyl glycolate, be hydrolyzed oxyacetic acid processed (GA) and there are great Development volue and wide market outlook.
The domestic production technique not having ripe eco-friendly methyl glycolate at present.The industrial chloroactic acid method that still adopts is produced.And chloroactic acid method production process is long, energy consumption is high, seriously polluted, cost is high, be badly in need of finding new operational path.Along with the important breakthrough of CO and this C1 route synthesis of chemicals of nitrous acid ester Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method (DMO), coal based synthetic gas is adopted to overcome the problems such as existing operational path is long, environment is unfriendly, maintenance of the equipment is difficult via prepared by dimethyl oxalate plus hydrogen methyl glycolate, have the plurality of advantages such as economy, environmental protection, the prospect of marketing is very optimistic.
The reaction of prepared by dimethyl oxalate plus hydrogen methyl glycolate and ethylene glycol is as follows:
(1)H
3COOC-COOCH
3+2H
2→HOCH
2-COOCH
3+CH
3OH
(2)HOCH
2-COOCH
3+2H
2→HOCH
2CH
2OH+CH
3OH
As can be seen from the above equation, Hydrogenation of Dimethyl Oxalate generates methyl glycolate, methyl glycolate hydrogenation generating glycol.Methyl glycolate is hydrogenation intermediate product, for the selectivity improving methyl glycolate need avoid the deep hydrogenation of methyl glycolate.
Patent CN101544539A discloses a kind of method generating polymer grade ethylene glycol and co-producing methyl glycolate.With coal, Sweet natural gas or residual oil for the obtained unstripped gas of raw material is through purifying treatment, carbon monoxide and hydrogen is obtained by pressure-variable adsorption, ethylene glycol and methyl glycolate is obtained through processes such as nitrosation reaction, oxonation, hydrogenation reaction, rectifying separation and tail gas clean-up process, by controlling hydrogenation reaction and the adjustable ethylene glycol of rectifying and methyl glycolate production ratio with auxiliary material industrial methanol, oxygen and nitrogen protoxide.Be analyzed document, this technique, mainly for the purpose of generating glycol, adopts Cu-SiO at hydrotreating stage
2or Cu-Cr2O
3or Cu-Zn-Al copper-based catalysts; According to document examples of implementation, this technique adopts larger hydrogen ester than 40 ~ 80 in hydrogenation workshop section, and when dimethyl oxalate transformation efficiency is greater than 99%, the selectivity of methyl glycolate is low to moderate 4%.
Patent CN102649743A discloses a kind of method of synthesizing methyl glycolate.Taking barkite as raw material, successively by being equipped with composite bed reactor and the catalyst exposure of copper oxide catalyst I and copper oxide catalyst I I, producing the reaction effluent containing methyl glycolate.Be analyzed document, this technique adopts dimethyl oxalate to be raw material and adopts the composite bed reactor containing two kinds of copper-based catalysts; According to document examples of implementation, the process employs larger hydrogen ester mol ratio 80 ~ 120 and higher reaction pressure 3.0 ~ 3.5MPa, dimethyl oxalate transformation efficiency is greater than 99%, and methyl glycolate selectivity is greater than 80%.
Patent CN102649745A discloses a kind of method of barkite gas phase hydrogenation methyl glycolate.Take barkite as raw material, with methyl alcohol, ethanol or water for terminator, contact with copper containing catalyst in fluidized-bed reactor, generate methyl glycolate.Be analyzed document, this technique adopts fluidized-bed reactor and uses copper-based catalysts; According to document examples of implementation, this technique adopts larger hydrogen ester mol ratio 40 ~ 50, and methyl glycolate selectivity is higher by 80 ~ 90%, but the transformation efficiency of dimethyl oxalate is all lower than 90%.
Patent CN102336666A, provide the preparation method of a kind of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, employing dimethyl oxalate is raw material, under the effect of argentiferous oxide catalyst, adopt continuous fixed bed reaction or continuous, methyl glycolate and ethylene glycol can be obtained.The method mainly introduces the making method of catalyzer, do not relate to technical process, be raw material when carrying out hydrogenation with dimethyl oxalate in this external hydrogenation technique, adopt larger hydrogen ester mol ratio 100, dimethyl oxalate transformation efficiency is greater than 99%, and methyl glycolate selectivity is greater than 80%.
Above-mentioned patent is obtain higher dimethyl oxalate transformation efficiency and methyl glycolate selectivity, adopts higher reaction pressure and larger hydrogen ester ratio, and energy consumption is large and high to equipment requirements.
Summary of the invention
Dimethyl oxalate low conversion rate and the low problem of methyl glycolate selectivity is there is for solving in prior art, the invention provides a kind of method of producing methyl glycolate, described method is focused on methyl glycolate and is produced full-range technique, adopt argentum-based catalyzer, (hydrogen ester mol ratio is comprised by optimizing materials (mass concentration of dimethyl oxalate) and Optimizing Technical, reaction pressure, temperature of reaction), while guarantee dimethyl oxalate transformation efficiency >99%, also improve the selectivity (>80%) of methyl glycolate, the methyl glycolate concentration that de-methyl glycolate column overhead distillates is greater than 99%, dimethyl oxalate content is lower than 0.5%, do not need design rectifying tower separating alcohol acid methyl esters and dimethyl oxalate, methyl glycolate can be avoided with dimethyl oxalate to be separated difficult problem, reduce energy consumption and equipment requirements.
For achieving the above object, technological design design of the present invention is as follows:
Produce a method for methyl glycolate, comprise the steps:
1) methanol solution of dimethyl oxalate is pressurized to reaction pressure, described reaction pressure counts 1.0 ~ 3.0MPa with gauge pressure, the methanol solution of the dimethyl oxalate after supercharging mixes with the unstripped gas containing hydrogen, obtain parallel feeding, in described parallel feeding, the mol ratio of hydrogen and dimethyl oxalate is 5 ~ 100, vaporizes, is warming up to 170 ~ 250 DEG C, enter reactor, under the effect of silver-containing catalyst, carry out hydrogenation reaction and obtain, containing methyl glycolate logistics, after heat exchange, entering Separate System of Water-jet; In described reactor, service temperature is 170 ~ 250 DEG C, and working pressure counts 1.0 ~ 3.0MPa with gauge pressure, dimethyl oxalate liquid hourly space velocity 0.3 ~ 1.0g/ (gCath);
2) 40 ~ 60 DEG C are condensed to containing methyl glycolate logistics, carry out one-level gas-liquid separation, isolated vapor condensation to 0 ~ 15 DEG C, carry out two grade low-temp gas-liquid separations, the liquid-phase mixing that isolated liquid phase and one-level gas-liquid separation obtain, obtains coarse ethanol acid methyl ester solution; Described one-level gas-liquid separation pressure counts 1.0 ~ 3.0MPa with gauge pressure; Described two grade low-temp gas-liquid separation pressure count 1.0 ~ 3.0MPa with gauge pressure;
3) coarse ethanol acid methyl ester solution enters eparating methanol tower rectifying, tower reactor heavy constituent enters the rectifying of de-methyl glycolate tower, described de-methyl glycolate column overhead overhead product is finished product methyl glycolate, and tower reactor heavy constituent enters de-ethylene glycol tower rectifying separation, collects tower reactor high boiling material.
Further, described reactor is isothermal fixed-bed reactor.
Separately, in described reactor, service temperature is 185 ~ 210 DEG C, and working pressure counts 1.5 ~ 2.0MPa with gauge pressure, described dimethyl oxalate liquid hourly space velocity 0.4 ~ 0.6g/ (gCath).
Separately have, step 1) gained carries out heat exchange containing methyl glycolate logistics and the described unstripped gas of hydrogen of containing, described unstripped gas comprises: step 2) the isolated gas phase of described two grade low-temp gas-liquid separation step after compression with the gas mixture of hydrogen.
Again, described containing in the unstripped gas of hydrogen, hydrogen volume mark is 80-95%, and all the other are carbon monoxide, carbonic acid gas, methane.
Further, methyl alcohol and dimethyl oxalate are uniformly mixed, mixing temperature is 35 ~ 55 DEG C, and pressure counts 0.4 ~ 0.5MPa with gauge pressure, obtains the methanol solution of described dimethyl oxalate.
And in the methanol solution of described dimethyl oxalate, dimethyl oxalate massfraction is 8 ~ 80wt%, and all the other are methyl alcohol.
Separately, in the methanol solution of described dimethyl oxalate, dimethyl oxalate massfraction is 50wt%.
Again, in described parallel feeding, the mol ratio of hydrogen and dimethyl oxalate is 5 ~ 20.
Further, step 3) described in eparating methanol tower tower top pressure count-0.08 ~-0.05MPa with gauge pressure, de-methyl glycolate column overhead pressure counts-0.09 ~-0.08MPa with gauge pressure, and de-ethylene glycol column overhead pressure counts-0.09 ~-0.08MPa with gauge pressure; Described eparating methanol tower overhead product is circulated to step 1) reuse as reaction raw materials.
Wherein, described silver-containing catalyst is catalyzer disclosed in Chinese patent CN102336666A embodiment.Described catalyzer adopts mesoporous silicon oxide to be carrier, take Ag as active ingredient or main active component, simultaneously containing one or more in Cu, Mg, Ca, Ba, Zn, Zr, Co, Cr, Ni, Mn, Sn, Au, Pt, Pd, Ru, Re as auxiliary agent, wherein the massfraction of Ag is 0.5 ~ 20%, the massfraction of auxiliary agent is 0.1 ~ 5%, and all the other are carrier.Described carrier is one or more in SBA-15, MCM-41, MCM-48, HMS, MSU.Described catalyzer adopts pickling process or sol-gel method preparation, and in hydrogen, carries out reduction treatment before using, and wherein, reductive condition is: hydrogen pressure 0.2 ~ 10.0MPa, hydrogen gas space velocity 100 ~ 3000h
-1, reduction temperature 120 ~ 400 DEG C, 2 ~ 36 hours recovery times.
Further, described silver-containing catalyst is the silver-containing catalyst in described Chinese patent CN102336666A described in embodiment 19.
Compared with prior art, beneficial effect of the present invention is:
A) the present invention adopts the methanol solution of dimethyl oxalate to replace pure dimethyl oxalate to carry out hydrogenation reaction as raw material, reduce the dividing potential drop of reaction process dimethyl oxalate in preparation and methyl glycolate, methyl glycolate deep hydrogenation generating glycol degree can be reduced, contribute to the selectivity improving methyl glycolate when the high conversion of dimethyl oxalate; Meanwhile, because pure dimethyl oxalate easily solidifies, the line clogging problem adopting the methanol solution of dimethyl oxalate that dimethyl oxalate can be avoided to solidify to cause;
B) lower hydrogen ester mol ratio 5 ~ 20 (mol ratio of hydrogen and dimethyl oxalate) is adopted when optimizing hydrogenation conditions, lower hydrogen ester mol ratio can reduce the dividing potential drop of hydrogen in reaction process, thus reduce methyl glycolate deep hydrogenation degree, the selectivity of methyl glycolate can be improved;
C) in step 3) rectification working process employing rectification under vacuum, reduces the service temperature of tower bottom of rectifying tower, can avoid occurring from polycondensation reaction during methyl glycolate high temperature, improve purity and the yield of methyl glycolate;
D) under the hydrogenation conditions optimized and rectifying condition, the methyl glycolate concentration that de-methyl glycolate column overhead distillates is greater than 99%, and dimethyl oxalate content, lower than 0.5%, can avoid methyl glycolate to be separated difficult problem with dimethyl oxalate;
E) adopt isothermal fixed-bed reactor, play the catalysis effectiveness of granular silver-containing catalyst;
F) select special silver-containing catalyst, specific surface area is large, useful load amount is low, low temperature active is high, is more conducive to reaction and carries out;
The Btu utilization of g) lower hydrogen ester mol ratio and the unstripped gas to reactor outlet, reduces energy consumption.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of production methyl glycolate of the present invention.
In Fig. 1, V101 is dimethyl oxalate dissolution kettle, P101 is liquid phase feeding pump, E101 is vaporizer, E102 is preheater before reactor, R101 is isothermal fixed-bed reactor, E103 is gas preheater, E201 is first-stage condenser, V201 is one-level knockout drum, E202 is secondary condenser, V202 is two grade low-temp knockout drums, C201 is recycle compressor, T301 is eparating methanol tower, P301 is de-methyl glycolate fresh feed pump, T302 is de-methyl glycolate tower, P302 is de-ethylene glycol fresh feed pump, T303 is de-ethylene glycol tower.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should comprise within the scope of the invention.
Embodiment 1
As shown in Figure 1, the method for production methyl glycolate of the present invention comprises the steps:
1) fresh methanol and dimethyl oxalate at dimethyl oxalate dissolution kettle V101 with mass ratio 1:1 stirring and dissolving, obtain the methanol solution of dimethyl oxalate, solvent temperature is 35 ~ 55 DEG C, pressure counts 0.4 ~ 0.5MPa with gauge pressure, bottom V101, liquid is out pressurized to reaction pressure through liquid phase feeding pump P101, described reaction pressure counts 1.5MPa with gauge pressure, liquid phase feeding pump P101 outlet streams 1 (i.e. the methanol solution of dimethyl oxalate) mixes with the ratio of mol ratio 1:8 with the hydrogen in the unstripped gas (wherein hydrogen volume mark 90%) containing hydrogen, obtain parallel feeding, after enter vaporizer E101, preheater E102 before vaporizer E101 outlet streams 2 dereaction device, be warming up to temperature of reaction 188 DEG C, enter isothermal fixed-bed reactor R101.In isothermal fixed-bed reactor R101, the principal reaction process of described hydrogenation reaction is (Cat represents catalyzer):
The silver-containing catalyst in Chinese patent CN102336666A described in embodiment 19 is adopted in described isothermal fixed-bed reactor R101, service temperature is 188 DEG C, hydrogen ester mol ratio (i.e. the mol ratio of hydrogen and dimethyl oxalate) is 8, pressure counts 1.5MPa with gauge pressure, and dimethyl oxalate liquid hourly space velocity is 0.5g/ (gCath).
Under silver-containing catalyst effect, except generating principal product methyl glycolate, also generate by-product carbinol, ethylene glycol, methyl-formiate, methylcarbonate and 1,2-butyleneglycol etc.Dimethyl oxalate transformation efficiency is 99.67%, and methyl glycolate selectivity is 84.78%, glycol selectivity 11.96%.
Logistics 4 be described isothermal fixed-bed reactor R101 out containing methyl glycolate logistics, after gas preheater E103 with unstripped gas 15 (i.e. the gas mixture of logistics 14 and hydrogen) heat exchange, obtain logistics 5 and to supply gas liquid separation circuit.
2) logistics 5 obtains logistics 6 through first-stage condenser E201 cooling, after one-level knockout drum V201 is separated, (pressure of separating tank is 1.45MPa again, temperature is 55 DEG C) obtain logistics 7, logistics 7 obtains logistics 9 through secondary condenser E202 cooling, after two grade low-temp knockout drum V202 are separated, (pressure of separating tank is 1.40MPa again, temperature is 10 DEG C) obtain logistics 11, logistics 11 part (logistics 13) reclaims, and a part (logistics 12) gas speeds to put.Logistics 13 obtains logistics 14 after gas compressor C201 compresses, and logistics 14 is circulated to described isothermal fixed-bed reactor R101 as reaction hydrogen (logistics 15) and participates in hydrogenation reaction together with raw hydrogen.The liquid stream 10 that the liquid stream 8 that described one-level knockout drum V201 is separated is separated with two grade low-temp knockout drum V202 merges into coarse ethanol acid methyl esters (logistics 17), and coarse ethanol acid methyl esters enters methyl glycolate refinement.
3) after coarse ethanol acid methyl esters (logistics 17) enters eparating methanol tower T301 (working pressure counts-0.08MPa with gauge pressure) rectifying separation, tower top distillates containing methyl alcohol, the logistics 18 (methanol content 99.7wt%) of methyl-formiate and ethanol.Logistics 18 part (logistics 19) can return described step 1) dimethyl oxalate dissolution kettle V101 reuses as liquid phase feed, and tower reactor heavy constituent obtains logistics 20 as the charging of de-methyl glycolate tower T302 (working pressure counts-0.09MPa with gauge pressure) after pump P301.Logistics 20 is after rectifying tower is separated, and tower top distillates the logistics 21 (methyl glycolate content 99.0wt%) containing methyl glycolate and dimethyl oxalate, and logistics 21, as product-collecting, obtains described methyl glycolate finished product.Tower reactor heavy constituent obtains logistics 22 as the charging of de-ethylene glycol tower T303 (working pressure counts-0.09MPa with gauge pressure) after pump P302.Logistics 22 is after rectifying tower is separated, and tower top distillates product ethylene glycol stream 23 (ethylene glycol content 98.5wt%), and tower reactor obtains logistics 24 (high boiling material), unified process after collecting.
Embodiment 2
In described isothermal fixed-bed reactor R101, hydrogen ester mol ratio is 20, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 98.02%, and methyl glycolate selectivity is 88.75%, glycol selectivity 9.32%.De-methyl glycolate column overhead methyl glycolate content is 97.8wt%.
Embodiment 3
In described isothermal fixed-bed reactor R101, hydrogen ester mol ratio is 40, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 96.88%, and methyl glycolate selectivity is 91.32%, glycol selectivity 6.84%.De-methyl glycolate column overhead methyl glycolate content is 94.4wt%.
Embodiment 4
In described isothermal fixed-bed reactor R101, reaction pressure counts 2.0MPa with gauge pressure, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.70%, and methyl glycolate selectivity is 71.14%, glycol selectivity 27.76%.De-methyl glycolate column overhead methyl glycolate content is 99.3wt%.
Embodiment 5
In described isothermal fixed-bed reactor R101, reaction pressure counts 2.5MPa with gauge pressure, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.9%, and methyl glycolate selectivity is 65.42%, glycol selectivity 32.76%.De-methyl glycolate column overhead methyl glycolate content is 99.5wt%.
Embodiment 6
Described isothermal fixed-bed reactor R101 dimethyl oxalate in preparation liquid hourly space velocity is 0.6g/ (gCath), and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 96.82%, and methyl glycolate selectivity is 87.44%, glycol selectivity 10.41%.De-methyl glycolate column overhead methyl glycolate content is 98.5wt%.
Embodiment 7
Described isothermal fixed-bed reactor R101 dimethyl oxalate in preparation liquid hourly space velocity is 0.8g/ (gCath), and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 90.82%, and methyl glycolate selectivity is 93.03%, glycol selectivity 5.21%.De-methyl glycolate column overhead methyl glycolate content is 90.5wt%.
Embodiment 8
Described isothermal fixed-bed reactor R101 service temperature is 196 DEG C, hydrogen ester dimethyl oxalate liquid hourly space velocity is 0.6g/ (gCath), and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.57%, methyl glycolate selectivity is 84.26%, glycol selectivity 13.75%.De-methyl glycolate column overhead methyl glycolate content is 99.3wt%.
Embodiment 9
Described isothermal fixed-bed reactor R101 service temperature is 204 DEG C, hydrogen ester dimethyl oxalate liquid hourly space velocity is 0.6g/ (gCath), and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.9%, methyl glycolate selectivity is 72.26%, glycol selectivity 24.85%.De-methyl glycolate column overhead methyl glycolate content is 99.5wt%.
Embodiment 10
Described dimethyl oxalate massfraction is 60%, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.65%, and methyl glycolate selectivity is 75.50%, glycol selectivity 22.42%.De-methyl glycolate column overhead methyl glycolate content is 99.4wt%.
Embodiment 11
Described dimethyl oxalate massfraction is 70%, and all the other are with embodiment 1, and dimethyl oxalate transformation efficiency is 99.71%, and methyl glycolate selectivity is 66.50%, glycol selectivity 31.22%.De-methyl glycolate column overhead methyl glycolate content is 99.4wt%.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. produce a method for methyl glycolate, it is characterized in that, comprise the steps:
1) methanol solution of dimethyl oxalate is pressurized to reaction pressure, described reaction pressure counts 1.0 ~ 3.0MPa with gauge pressure, the methanol solution of the dimethyl oxalate after supercharging mixes with the unstripped gas containing hydrogen, obtain parallel feeding, in described parallel feeding, the mol ratio of hydrogen and dimethyl oxalate is 5 ~ 100, vaporizes, is warming up to 170 ~ 250 DEG C, enter reactor, under the effect of silver-containing catalyst, carry out hydrogenation reaction and obtain, containing methyl glycolate logistics, after heat exchange, entering Separate System of Water-jet; In described reactor, service temperature is 170 ~ 250 DEG C, and working pressure counts 1.0 ~ 3.0MPa with gauge pressure, dimethyl oxalate liquid hourly space velocity 0.3 ~ 1.0g/ (gCath);
2) 40 ~ 60 DEG C are condensed to containing methyl glycolate logistics, carry out one-level gas-liquid separation, isolated vapor condensation to 0 ~ 15 DEG C, carry out two grade low-temp gas-liquid separations, the liquid-phase mixing that isolated liquid phase and one-level gas-liquid separation obtain, obtains coarse ethanol acid methyl ester solution; Described one-level gas-liquid separation pressure counts 1.0 ~ 3.0MPa with gauge pressure; Described two grade low-temp gas-liquid separation pressure count 1.0 ~ 3.0MPa with gauge pressure;
3) coarse ethanol acid methyl ester solution enters eparating methanol tower rectifying, tower reactor heavy constituent enters the rectifying of de-methyl glycolate tower, described de-methyl glycolate column overhead overhead product is finished product methyl glycolate, and tower reactor heavy constituent enters de-ethylene glycol tower rectifying separation, collects tower reactor high boiling material.
2., according to the method for claim 1 or described production methyl glycolate, it is characterized in that, described reactor is isothermal fixed-bed reactor.
3. the method for production methyl glycolate according to claim 1 and 2, it is characterized in that, in described reactor, service temperature is 185 ~ 210 DEG C, and working pressure counts 1.5 ~ 2.0MPa with gauge pressure, described dimethyl oxalate liquid hourly space velocity 0.4 ~ 0.6g/ (gCath).
4. the method for production methyl glycolate according to claim 1, it is characterized in that, step 1) gained carries out heat exchange containing methyl glycolate logistics and the described unstripped gas of hydrogen of containing, described unstripped gas comprises: step 2) the isolated gas phase of described two grade low-temp gas-liquid separation step after compression with the gas mixture of hydrogen.
5. the method for the production methyl glycolate according to claim 1 or 4, is characterized in that, described containing in the unstripped gas of hydrogen, hydrogen volume mark is 80-95%, and all the other are carbon monoxide, carbonic acid gas, methane.
6. the method for production methyl glycolate according to claim 1, is characterized in that, methyl alcohol and dimethyl oxalate is uniformly mixed, and mixing temperature is 35 ~ 55 DEG C, and pressure counts 0.4 ~ 0.5MPa with gauge pressure, obtains the methanol solution of described dimethyl oxalate.
7., according to the method for claim 1 or described production methyl glycolate, it is characterized in that, in the methanol solution of described dimethyl oxalate, dimethyl oxalate massfraction is 8 ~ 80wt%, and all the other are methyl alcohol.
8. the method for production methyl glycolate according to claim 6, is characterized in that, in the methanol solution of described dimethyl oxalate, dimethyl oxalate massfraction is 50wt%.
9. the method for production methyl glycolate according to claim 1, is characterized in that, in described parallel feeding, the mol ratio of hydrogen and dimethyl oxalate is 5 ~ 20.
10. a kind of method of producing methyl glycolate according to claim 1, it is characterized in that, step 3) described in eparating methanol tower tower top pressure count-0.08 ~-0.05MPa with gauge pressure, de-methyl glycolate column overhead pressure counts-0.09 ~-0.08MPa with gauge pressure, and de-ethylene glycol column overhead pressure counts-0.09 ~-0.08MPa with gauge pressure; Described eparating methanol tower overhead product is circulated to step 1) reuse as reaction raw materials.
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Cited By (12)
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| CN105348102A (en) * | 2015-12-16 | 2016-02-24 | 西南化工研究设计院有限公司 | Heat-insulation reaction system and process for preparing glycolate through oxalate hydrogenation |
| CN109134258A (en) * | 2017-06-28 | 2019-01-04 | 上海浦景化工技术股份有限公司 | A kind of product separating technology of prepared by dimethyl oxalate plus hydrogen methyl glycollate |
| CN111454151A (en) * | 2020-04-26 | 2020-07-28 | 宁波中科远东催化工程技术有限公司 | Method for vaporizing dimethyl oxalate |
| CN111646895A (en) * | 2020-07-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Preparation method of glycolic acid or glycolate |
| CN112028768A (en) * | 2020-09-08 | 2020-12-04 | 南京延长反应技术研究院有限公司 | Reaction system and method for preparing glycolate through oxalate hydrogenation |
| CN112206775A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and application of prepared catalyst |
| CN112209832A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for synthesizing glycolate from oxalate |
| CN112206774A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN112209831A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester |
| CN112409493A (en) * | 2020-08-12 | 2021-02-26 | 浙江工业大学 | Recombinant fusion enzyme and application thereof in synthesis of methyl glyoxylate |
| CN112469759A (en) * | 2018-10-29 | 2021-03-09 | 上海浦景化工技术股份有限公司 | Glycolide production with low solid residue |
| WO2022052223A1 (en) * | 2020-09-08 | 2022-03-17 | 南京延长反应技术研究院有限公司 | Intensified microinterface preparation system and method for polyglycolic acid |
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| CN111454151A (en) * | 2020-04-26 | 2020-07-28 | 宁波中科远东催化工程技术有限公司 | Method for vaporizing dimethyl oxalate |
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| CN112409493B (en) * | 2020-08-12 | 2022-09-30 | 浙江工业大学 | Recombinant fusion enzyme and application thereof in synthesis of methyl glyoxylate |
| CN112409493A (en) * | 2020-08-12 | 2021-02-26 | 浙江工业大学 | Recombinant fusion enzyme and application thereof in synthesis of methyl glyoxylate |
| WO2022052223A1 (en) * | 2020-09-08 | 2022-03-17 | 南京延长反应技术研究院有限公司 | Intensified microinterface preparation system and method for polyglycolic acid |
| WO2022052222A1 (en) * | 2020-09-08 | 2022-03-17 | 南京延长反应技术研究院有限公司 | Reaction system and method for preparing glycolate by using oxalate hydrogenation |
| CN112028768A (en) * | 2020-09-08 | 2020-12-04 | 南京延长反应技术研究院有限公司 | Reaction system and method for preparing glycolate through oxalate hydrogenation |
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