CN102649742A - Method for increasing selectivity of glycollic acid ester - Google Patents
Method for increasing selectivity of glycollic acid ester Download PDFInfo
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- CN102649742A CN102649742A CN201110045219XA CN201110045219A CN102649742A CN 102649742 A CN102649742 A CN 102649742A CN 201110045219X A CN201110045219X A CN 201110045219XA CN 201110045219 A CN201110045219 A CN 201110045219A CN 102649742 A CN102649742 A CN 102649742A
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Abstract
The invention relates to a method for increasing selectivity of glycollic acid ester. The technical problem of low selectivity of the glycollic acid ester in the prior art is solved. The method comprises the following steps of: taking oxalate as a raw material, and contacting the raw material with a copper-containing oxide catalyst 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 the reaction is started by the copper-containing oxide catalyst under oxide state, and on the basis of weight part of the catalyst, the copper-containing oxide catalyst comprises 10-60 weight parts of copper and copper oxide components. 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 optionally method of a kind of raising ethyl glycolate, particularly improve optionally method of ethyl glycolate about dimethyl oxalate hydrogenation or oxalic acid diethyl ester hydrogenation.
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 that C-1 chemistry is produced 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 one 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 optionally method of a kind of new raising ethyl glycolate 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 raising ethyl glycolate is method optionally, is raw material with the barkite, is 100～210 ℃ in temperature of reaction, and weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 10～100: 1, and reaction pressure is under the condition of 0.5～6.0MPa, and raw material contacts with the copper oxide catalyzer, and reaction generates the reaction effluent that contains ethyl glycolate;
Wherein, the copper oxide catalyzer starts reaction with the oxide compound state; The copper oxide catalyzer, in the catalyst weight umber, copper and oxide component parts by weight thereof are 10～60 parts; Preferred weight umber scope is 15～50 parts.
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 2～40MPa.
Technique scheme medium-height grass acid esters 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 finds in research process, equally for copper class catalyzer, Cu
2 +The selectivity of reaction that generates ethyl glycolate for the catalyzer in active site for the barkite hydrogenation is higher; And for the reacting phase of further generation terepthaloyl moietie to a little less than; Especially at the driving initial stage, catalyzer starts reaction with the state of oxidation, and the selectivity of ethyl glycolate has more significantly and improves.Technical scheme of the present invention is reacted the raw material barkite under the state of oxidation with copper oxide catalyzer contact start, both guaranteed transformation efficiency, has improved selectivity again.
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
-1, hydrogen/ester mol ratio is 10～100: 1, and reaction pressure is 0.5～6.0MPa, and raw material contacts with the copper oxide catalyzer, and reaction generates the reaction effluent that contains ethyl glycolate; The copper oxide catalyzer starts reaction with the oxide compound state; The copper oxide catalyzer, in the catalyst weight umber, copper and oxide component parts by weight thereof are that the transformation efficiency of barkite can be greater than 90% under 10～60 parts the condition, 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 active copper 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
2Catalyzer.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the dimethyl oxalate, be 180 ℃ in temperature of reaction, weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the 3.0MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of dimethyl oxalate is 82%, the selectivity of NSC 27786 is 86.4%.
[embodiment 2]
According to the copper oxide catalyzer that each Step By Condition of [embodiment 1] makes, its cupric oxide composition weight umber is 28 parts.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the dimethyl oxalate, be 140 ℃ in temperature of reaction, weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 50: 1, and reaction pressure is under the 5.0MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of dimethyl oxalate is 80.1%, the selectivity of ethyl glycolate is 82.3%.
[embodiment 3]
According to the copper oxide catalyzer that each Step By Condition of [embodiment 1] makes, its cupric oxide composition weight umber is 25 parts.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the dimethyl oxalate, be 190 ℃ in temperature of reaction, weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the 4.0MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of dimethyl oxalate is 90.8%, the selectivity of ethyl glycolate is 91.8%.
[embodiment 4]
According to the copper oxide catalyzer that each Step By Condition of [embodiment 1] makes, its cupric oxide composition weight umber is 40 parts.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the dimethyl oxalate, be 210 ℃ in temperature of reaction, weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the 3.0MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethyl glycolate is 89.8%.
[embodiment 5]
The copper oxide catalyzer that makes according to each Step By Condition of [embodiment 1], and introduce the nickel oxide auxiliary agent, its cupric oxide composition weight umber is 50 parts, the nickel oxide parts by weight are 5 parts.
Take by weighing the CuO+NiO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the oxalic acid diethyl ester, be 250 ℃ in temperature of reaction, weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 120: 1, and reaction pressure is under the 2.5MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 98.5%, the selectivity of ethyl glycolate is 92.2%.
[embodiment 6]
According to the copper oxide catalyzer that each Step By Condition of [embodiment 1] makes, its cupric oxide composition weight umber is 30 parts.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the oxalic acid diethyl ester, be 230 ℃ in temperature of reaction, weight space velocity is 2 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the 35MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 100%, the selectivity of ethyl glycolate is 91.4%.
[embodiment 7]
According to the copper oxide catalyzer that each Step By Condition of [embodiment 1] makes, its cupric oxide composition weight umber is 18 parts.
Take by weighing the CuO/SiO that makes
2Catalyzer 200 gram pack into diameter be 24 millimeters tubular reactor in, be raw material with the dimethyl oxalate, be 200 ℃ in temperature of reaction, weight space velocity is 1.0 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the 3.0MPa condition, and raw material contacts with the copper oxide catalyzer, reacts, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethyl glycolate is 88.7%.
[Comparative Examples 1]
According to [embodiment 1] identical reaction conditions and raw material; Just before the catalyst reaction through hydrogen 300 ℃ be reduced to metallic copper after; Feed dimethyl oxalate again and react, its reaction result is: the transformation efficiency of dimethyl oxalate is 60.1%, and the selectivity of ethyl glycolate is 80%.
Claims (5)
1. one kind is improved optionally method of ethyl glycolate, is raw material with the barkite, is 100～210 ℃ in temperature of reaction, and weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 10～100: 1, and reaction pressure is under the condition of 0.5～6.0MPa, and raw material contacts with the copper oxide catalyzer, and reaction generates the reaction effluent that contains ethyl glycolate;
Wherein, the copper oxide catalyzer starts reaction with the oxide compound state; The copper oxide catalyzer, in the catalyst weight umber, copper and oxide component parts by weight thereof are 10～60 parts.
2. according to the said raising ethyl glycolate of claim 1 method optionally, 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 said raising ethyl glycolate of claim 2 method optionally, 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 said raising ethyl glycolate of claim 1 method optionally, it is characterized in that the copper oxide catalyzer, in the catalyst weight umber, copper and oxide component parts by weight thereof are 15～50 parts.
5. according to the said raising ethyl glycolate of claim 1 method optionally, it is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
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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 |
| 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 |
| CN105396584A (en) * | 2014-08-27 | 2016-03-16 | 中国石油化工股份有限公司 | Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst |
| CN109569655A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Hydrogenation of oxalate for preparing for ethyl glycolate method |
| 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 |
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| US4409395A (en) * | 1981-01-26 | 1983-10-11 | Ube Industries, Ltd. | Process for the production of glycollic acid esters |
| CN101138730A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for oxalic ester hydrogenation synthesizing of glycolate and method of preparing the same |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101700496A (en) * | 2009-10-21 | 2010-05-05 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
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2011
- 2011-02-25 CN CN201110045219.XA patent/CN102649742B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4409395A (en) * | 1981-01-26 | 1983-10-11 | Ube Industries, Ltd. | Process for the production of glycollic acid esters |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101138730A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for oxalic ester hydrogenation synthesizing of glycolate and method of preparing the same |
| CN101700496A (en) * | 2009-10-21 | 2010-05-05 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
Cited By (9)
| 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 |
| CN104926657B (en) * | 2014-03-17 | 2018-01-09 | 中国石油化工股份有限公司 | The method of oxalate gas phase hydrogenation synthesizing alcohol acid esters |
| CN105396584A (en) * | 2014-08-27 | 2016-03-16 | 中国石油化工股份有限公司 | Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst |
| CN105396584B (en) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage |
| CN109569655A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Hydrogenation of oxalate for preparing for ethyl glycolate method |
| 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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