CN102649743A - Method for synthesizing glycollic acid ester - Google Patents
Method for synthesizing glycollic acid ester Download PDFInfo
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- CN102649743A CN102649743A CN201110045233XA CN201110045233A CN102649743A CN 102649743 A CN102649743 A CN 102649743A CN 201110045233X A CN201110045233X A CN 201110045233XA CN 201110045233 A CN201110045233 A CN 201110045233A CN 102649743 A CN102649743 A CN 102649743A
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Abstract
The invention relates to a method for synthesizing glycollic acid ester. The technical problem of low selectivity of the glycollic acid ester in the prior art is solved. The invention adopts the technical scheme that the method comprises the following steps of: taking oxalate as a raw material, and contacting the raw material with a catalyst through a compound bed reactor filled with a copper-containing oxide catalyst I and a copper-containing oxide catalyst II in turn, under the conditions of reaction temperature at 100-210 DEG C, weight hourly space velocity at 0.2-5 per hour, mole ratio of hydrogen to ester at (10-100):1 and reaction pressure at 0.5-6.0MPa, thereby generating a reaction effluent containing the glycollic acid ester, wherein on the basis of the weight part of the catalyst, the weight part of the copper oxide of the copper-containing oxide catalyst I is less than the weight part of the copper oxide of the copper-containing oxide catalyst II. According to the technical scheme, the problem is more efficiently solved. The method is suitable for the industrial production for increasing the yield of glycollic acid ester.
Description
Technical field
The present invention relates to a kind of method of synthesizing alcohol acid esters, particularly about the method for dimethyl oxalate hydrogenation or oxalic acid diethyl ester hydrogenation synthesizing of glycolate ester.
Background technology
Ethyl glycolate is with its distinctive molecular structure: have a-H, hydroxyl and ester group functional group simultaneously, make it have the chemical property of pure and mild ester concurrently, oxonation, hydrolysis reaction, oxidizing reaction etc. can take place, become a kind of important chemical material.Ethyl glycolate is the fine solvent of many Mierocrystalline celluloses, resin, rubber.Its derived product oxyacetic acid, glycocoll, methyl-malonate and oxoethanoic acid etc. also are with a wide range of applications.
At present, the domestic production technique that does not have sophisticated eco-friendly ethyl glycolate.Still adopt chloroactic acid method production, its technology is that Mono Chloro Acetic Acid is mixed, stirs with soda lye.On boiling water bath, heat, reduction vaporization, filtering sodium-chlor, in oil bath, heat paste liquid, add the methyl alcohol and the vitriol oil afterwards, reflux NSC 27786, with yellow soda ash neutralization, placement is spent the night, vacuum fractionation gets the product ethyl glycolate.Its production process is long, energy consumption is high, seriously polluted, cost is high, suddenly waits to seek new operational path.Opened up the new important channel of carbon-chemical prodn barkite by CO and nitrous acid ester synthesis of oxalic ester by gaseous catalysis.And then under katalysis, the barkite hydrogenation is come the ethanol production acid esters.Reported the new development of ethyl glycolate both at home and abroad successively.As in German Patent 45603, use the Cr/Cu catalyzer that makes by cupric and trivalent chromium that hydrogenation of oxalate for preparing is got the hexanol acid esters.The Cr/Cu catalyzer is the catalyzer with ester class hydrogenation that is widely known by the people.But the inconvenience in industry is used has seriously reduced in fact with being worth.Chromium is one of basal component of this catalyzer, but will it efficiently and fully be extracted very difficulty from used catalyst.Even the chromium of trace also has very big toxic action to human body, and this used catalyst is abandoned causing the serious environmental pollution.
Document CN200910201319.X discloses a kind of preparation method of ethyl glycolate, is raw material with the HZSM5 molecular sieve, at NH
4NO
3Reflux in the solution; The solid formation that filtration is obtained places the resistance furnace activation, obtains deactivated catalyst, is raw material again with the glyoxal water solution; Deactivated catalyst carries out esterification with C4-C8 unit alcohol under nitrogen atmosphere, from reaction product, collect the title product ethyl glycolate then.But this method flow growth process is complicated, and the selectivity of ethyl glycolate is lower simultaneously, usually in 80%.
Under situation about being becoming tight petroleum resources day, development oil replacement resource has become common recognition, and the resource general layout of China can be summarized as few oil, weak breath, many coals.Development carbon-chemical industry not only can make full use of Sweet natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental stress, is unusual important field of research.With the carbon monoxide is the feedstock production barkite, then hydrogenation of oxalate for preparing is equipped with ethyl glycolate and is a very attractive Coal Chemical Industry route, significant.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of ethyl glycolate selectivity that exists in the method for document in the past, and a kind of method of new synthesizing alcohol acid esters is provided.This method has the high advantage of ethyl glycolate selectivity.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of synthesizing alcohol acid esters is a raw material with the barkite, is 100～210 ℃ in temperature of reaction, and weight space velocity is 0.2～5 hour
-1Hydrogen/ester mol ratio is 10～100: 1; Reaction pressure is under the condition of 0.5～6.0MPa, and raw material contacts with catalyzer through the composite bed reactor that copper oxide catalyst I and copper oxide catalyst I I are housed successively, generates the reaction effluent that contains ethyl glycolate;
Wherein, in the catalyst weight umber, the parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than the parts by weight of oxide compound of the copper of copper oxide catalyst I I; The filling ratio of copper oxide catalyst I and copper oxide catalyst I I is 0.1～3: 1.
The reaction conditions preferable range is in the technique scheme: 130～200 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～80: 1, reaction pressure is 1.5～4.0MPa.Reaction conditions more preferably scope is: 140～200 ℃ of temperature of reaction, weight space velocity are 0.4～3 hour
-1, hydrogen/ester mol ratio is 30～70: 1, reaction pressure is 2～4.0MPa.
Copper oxide catalyst I in the technique scheme is 5～60 parts in catalyst weight umber copper oxide; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 0.2～20 part of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.Barkite is preferably selected from dimethyl oxalate or oxalic acid diethyl ester, more preferably is selected from dimethyl oxalate.
As everyone knows, barkite hydrogenation process is typical cascade reaction, and the first step barkite at first hydrogenation generates ethyl glycolate; Ethyl glycolate can make terepthaloyl moietie by repeated hydrogenation then; The reaction process in two steps is thermopositive reaction, and in addition, ethyl glycolate can generate ethanol by further hydrogenation under proper condition.Therefore, in order to obtain the purpose product of ethyl glycolate, how controlling the further of cascade reaction is the key of technology.The present inventor is surprised to find in research process; Adopt composite bed reactor; Loading catalyst I and catalyst I I successively; And when the parts by weight of oxide compound that make the copper of copper oxide catalyst I (reactor inlet end) are lower than the parts by weight of oxide compound of copper of copper oxide catalyst I I, when feed stock conversion can be guaranteed, keep higher glycol selectivity.
Adopting technical scheme of the present invention, is raw material with the barkite, is 100～210 ℃ in temperature of reaction, and weight space velocity is 0.2～5 hour
-1Hydrogen/ester mol ratio is 10～100: 1; Reaction pressure is under the condition of 0.5～6.0MPa, and raw material contacts with catalyzer through the composite bed reactor that copper oxide catalyst I and copper oxide catalyst I I are housed successively, generates the reaction effluent that contains ethyl glycolate; Wherein, in the catalyst weight umber, the parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than the parts by weight of oxide compound of the copper of copper oxide catalyst I I; The filling ratio of copper oxide catalyst I and copper oxide catalyst I I is that the transformation efficiency of oxalate diester can be greater than 90% under 0.1～3: 1 the condition, and the selectivity of ethyl glycolate can obtain better technical effect greater than 85%.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Taking by weighing specific surface is silica support 500 grams of 400 meters squared per gram; According to 35 parts of cupric oxide content configuration catalyzer; Its step is following: choose cupric nitrate; Be made into steeping fluid according to the Cu charge capacity, silica support is flooded 24 hours in this solution after, vacuum-drying at room temperature 12 hours solids.Solid was descended dry 12 hours at 120 ℃, 450 ℃ of roastings made required CuO/SiO in 4 hours afterwards again
2Catalyst I.
Make catalyst I I according to above-mentioned steps and condition, just among the catalyst I I according to catalyst weight umber meter, cupric oxide content is 40 parts.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 1: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the dimethyl oxalate is raw material, is 180 ℃ in temperature of reaction, and weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 60: 1, reaction pressure is 3.0MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of dimethyl oxalate is 80%, and the selectivity of NSC 27786 is 86.4%.
[embodiment 2]
According to copper oxide catalyst I and the copper oxide catalyst I I that each Step By Condition of [embodiment 1] makes, wherein,, it is 40 parts in catalyst weight umber copper oxide for the copper oxide catalyst I; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 5 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 0.5: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the dimethyl oxalate is raw material, is 140 ℃ in temperature of reaction, and weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 50: 1, reaction pressure is 5.0MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of dimethyl oxalate is 80.1%, and the selectivity of ethyl glycolate is 82.3%.
[embodiment 3]
According to copper oxide catalyst I and the copper oxide catalyst I I that each Step By Condition of [embodiment 1] makes, wherein,, it is 45 parts in catalyst weight umber copper oxide for the copper oxide catalyst I; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 8 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 0.3: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the dimethyl oxalate is raw material, is 190 ℃ in temperature of reaction, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 60: 1, reaction pressure is 4.0MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of dimethyl oxalate is 99.8%, and the selectivity of ethyl glycolate is 94.8%.
[embodiment 4]
According to copper oxide catalyst I and the copper oxide catalyst I I that each Step By Condition of [embodiment 1] makes, wherein,, it is 50 parts in catalyst weight umber copper oxide for the copper oxide catalyst I; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 10 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 0.8: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the dimethyl oxalate is raw material, is 210 ℃ in temperature of reaction, and weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 70: 1, reaction pressure is 3.0MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethyl glycolate is 91.8%.
[embodiment 5]
The copper oxide catalyst I and the copper oxide catalyst I I that make according to each Step By Condition of [embodiment 1]; Wherein, For the copper oxide catalyst I, it is 20 parts in catalyst weight umber copper oxide, simultaneously; The oxide compound that also contains barium, its oxide compound in catalyst I parts by weight barium is 5 parts; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 20 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 1.5: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the oxalic acid diethyl ester is raw material, is 250 ℃ in temperature of reaction, and weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 120: 1, reaction pressure is 2.5MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 98.5%, and the selectivity of ethyl glycolate is 92.2%.
[embodiment 6]
According to copper oxide catalyst I and the copper oxide catalyst I I that each Step By Condition of [embodiment 1] makes, wherein,, it is 30 parts in catalyst weight umber copper oxide for the copper oxide catalyst I; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 15 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 3: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the oxalic acid diethyl ester is raw material, is 230 ℃ in temperature of reaction, and weight space velocity is 2 hours
-1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 3.5MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethyl glycolate is 89.4%.
[embodiment 7]
According to copper oxide catalyst I and the copper oxide catalyst I I that each Step By Condition of [embodiment 1] makes, wherein,, it is 25 parts in catalyst weight umber copper oxide for the copper oxide catalyst I; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 3 parts of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight is 100 grams, and the filling ratio of catalyst I and catalyst I I is 4: 1, in reactor drum, pack into successively catalyst I I and catalyst I (entry position).With the dimethyl oxalate is raw material, is 200 ℃ in temperature of reaction, and weight space velocity is 1.0 hours
-1, hydrogen/ester mol ratio is 80: 1, reaction pressure is 3.0MPa; Raw material contacts with catalyzer through the composite bed reactor that catalyst I and catalyst I I are housed successively; React, its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethyl glycolate is 94.7%.
[Comparative Examples 1]
According to [embodiment 7] identical reaction conditions and raw material, just catalyzer only adopts copper oxide catalyst I I, and its reaction result is: the transformation efficiency of dimethyl oxalate is 95.1%, and the selectivity of ethyl glycolate is 87.1%.
Claims (5)
1. the method for a synthesizing alcohol acid esters is a raw material with the barkite, is 100～210 ℃ in temperature of reaction, and weight space velocity is 0.2～5 hour
-1Hydrogen/ester mol ratio is 10～100: 1; Reaction pressure is under the condition of 0.5～6.0MPa, and raw material contacts with catalyzer through the composite bed reactor that copper oxide catalyst I and copper oxide catalyst I I are housed successively, generates the reaction effluent that contains ethyl glycolate;
Wherein, in the catalyst weight umber, the parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than the parts by weight of oxide compound of the copper of copper oxide catalyst I I; The filling ratio of copper oxide catalyst I and copper oxide catalyst I I is 0.1～3: 1.
2. according to the method for the said synthesizing alcohol acid esters of claim 1, it is characterized in that 130～200 ℃ of temperature of reaction, weight space velocity is 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～80: 1, reaction pressure is 1.5～4.0MPa.
3. according to the method for the said synthesizing alcohol acid esters of claim 2, it is characterized in that 140～200 ℃ of temperature of reaction, weight space velocity is 0.4～3 hour
-1, hydrogen/ester mol ratio is 30～70: 1, reaction pressure is 2～4.0MPa.
4. according to the method for the said synthesizing alcohol acid esters of claim 1, it is characterized in that the copper oxide catalyst I, is 5～60 parts in catalyst weight umber copper oxide; The parts by weight of the oxide compound of the copper of copper oxide catalyst I are lower than 0.2～20 part of the parts by weight of oxide compound of the copper of copper oxide catalyst I I.
5. according to the method for the said synthesizing alcohol acid esters of claim 1, it is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110045233.XA CN102649743B (en) | 2011-02-25 | 2011-02-25 | Method for synthesizing glycollic acid ester |
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| CN201110045233.XA CN102649743B (en) | 2011-02-25 | 2011-02-25 | Method for synthesizing glycollic acid ester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109093A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for synthesizing glycolate through hydrogenating oxalate |
| CN104926657A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for synthesizing glycolic acid ester by gas-phase hydrogenation of oxalate |
| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0614875A1 (en) * | 1993-03-12 | 1994-09-14 | Ube Industries, Ltd. | Method of producing a glycolic acid ester |
| CN1409698A (en) * | 1999-12-10 | 2003-04-09 | 三菱丽阳株式会社 | Method for producing methacrylic acid |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
| CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
-
2011
- 2011-02-25 CN CN201110045233.XA patent/CN102649743B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0614875A1 (en) * | 1993-03-12 | 1994-09-14 | Ube Industries, Ltd. | Method of producing a glycolic acid ester |
| CN1409698A (en) * | 1999-12-10 | 2003-04-09 | 三菱丽阳株式会社 | Method for producing methacrylic acid |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
| CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109093A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for synthesizing glycolate through hydrogenating oxalate |
| CN104109093B (en) * | 2013-04-16 | 2016-04-13 | 中国石油化工股份有限公司 | The method of oxalic ester hydrogenation synthesizing of glycolate |
| CN104926657A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for synthesizing glycolic acid ester by gas-phase hydrogenation of oxalate |
| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN110871071B (en) * | 2018-09-04 | 2022-02-01 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
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