CN102649743B - Method for synthesizing glycollic acid ester - Google Patents
Method for synthesizing glycollic acid ester Download PDFInfo
- Publication number
- CN102649743B CN102649743B CN201110045233.XA CN201110045233A CN102649743B CN 102649743 B CN102649743 B CN 102649743B CN 201110045233 A CN201110045233 A CN 201110045233A CN 102649743 B CN102649743 B CN 102649743B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- copper
- copper oxide
- weight
- oxide catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 Hydrogenation of Dimethyl Oxalate or oxalic acid diethyl ester hydrogenation synthesizing of glycolate ester.
Background technology
Ethyl glycolate is with its unique molecular structure: have a-H, hydroxyl and ester group functional group simultaneously, make it have the chemical property of alcohol and ester concurrently, oxonation, hydrolysis reaction, oxidizing reaction etc. can occur, become a kind of important industrial chemicals.Ethyl glycolate is the fine solvent of many Mierocrystalline celluloses, resin, rubber.Its derived product oxyacetic acid, glycine, dimethyl malonate and oxoethanoic acid etc. are also with a wide range of applications.
At present, the domestic production technique that there is no ripe eco-friendly ethyl glycolate.Still adopt chloroactic acid method to produce, its technique is that Mono Chloro Acetic Acid is mixed, stirred evenly with soda lye.On boiling water bath, heat, reduction vaporization, filtering sodium-chlor heats to obtain paste liquid in oil bath, adds afterwards methyl alcohol and the vitriol oil, the methyl glycolate that refluxes to obtain, with sodium carbonate neutralization, placement is spent the night, and vacuum fractionation obtains product ethyl glycolate.Its production process is long, energy consumption is high, seriously polluted, cost is high, suddenly waits to find new operational path.By CO and nitrous acid ester synthesis of oxalic ester by gaseous catalysis, opened up the new important channel of carbon-chemical production barkite.And then under katalysis, barkite hydrogenation is carried out to ethanol production acid esters.Reported successively the new development of ethyl glycolate both at home and abroad.As in German Patent 45603, use the Cr/Cu catalyzer being made by cupric and trivalent chromium that hydrogenation of oxalate for preparing is got to hexanol acid esters.Cr/Cu catalyzer be widely known by the people by the catalyzer of ester class hydrogenation.But the inconvenience in industrial application has seriously reduced its practical value.Chromium is one of basal component of this catalyzer, but it efficiently and fully will be extracted from used catalyst very difficult.Even if the chromium of trace also has very large toxic action to human body, and this used catalyst is abandoned and will cause serious environmental pollution.
Document CN200910201319.X discloses a kind of preparation method of ethyl glycolate, take HZSM5 molecular sieve as raw material, at NH
4nO
3in solution, reflux, the solid formation that filtration is obtained is placed in resistance furnace and activates, and obtains deactivated catalyst, then take glyoxal water solution as raw material, deactivated catalyst carries out esterification with C4-C8 unit alcohol under nitrogen atmosphere, then from reaction product, collects target product ethyl glycolate.But the method long flow path process is complicated, the selectivity of ethyl glycolate is lower simultaneously, conventionally in 80%.
The in the situation that of being becoming tight in 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.The carbon monoxide of take is prepared barkite as raw material, then hydrogenation of oxalate for preparing is a very attractive Coal Chemical Industry Route for ethyl glycolate, significant.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of ethyl glycolate selectivity existing in the method for previous literature, and a kind of method of new synthesizing alcohol acid esters is provided.The method has the high advantage of ethyl glycolate selectivity.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of synthesizing alcohol acid esters, take barkite as raw material, and in temperature of reaction, be 100～210 ℃, 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 with the composite bed reactor of copper oxide catalyst I I by copper oxide catalyst I is housed successively, generates the reaction effluent containing ethyl glycolate;
Wherein, in 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 the 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.
In technique scheme, reaction conditions preferable range is: 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.Reaction conditions more preferably scope is: 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.
Copper oxide catalyst I in technique scheme, the catalyst weight umber copper oxide of take is 5～60 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.Barkite is preferably selected from dimethyl oxalate or oxalic acid diethyl ester, is more preferably selected from dimethyl oxalate.
As everyone knows, barkite hydrogenation process is typical cascade reaction, and the first step barkite first hydrogenation generates ethyl glycolate, then ethyl glycolate can make ethylene glycol by repeated hydrogenation, the reaction process of 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 object product of ethyl glycolate, how controlling the further of cascade reaction is the key of technology.Present inventor is surprised to find in research process, adopt composite bed reactor, loading catalyst I and catalyst I I successively, and the parts by weight of oxide compound of copper that make copper oxide catalyst I (reactor inlet end) are during lower than the parts by weight of the oxide compound of the 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, take barkite as raw material, 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 with the composite bed reactor of copper oxide catalyst I I by copper oxide catalyst I is housed successively, generates the reaction effluent containing ethyl glycolate; Wherein, in 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 the 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 under 0.1～3: 1 condition, the transformation efficiency of oxalate diester can be greater than 90%, and the selectivity of ethyl glycolate can be greater than 85%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take specific surface and be 500 grams of the silica supports of 400 meters squared per gram, according to 35 parts of cupric oxide content configuration catalyzer, its step is as follows: choose cupric nitrate, according to Cu charge capacity, be made into steeping fluid, silica support is flooded in this solution after 24 hours, at room temperature vacuum-drying obtains solids for 12 hours.Again solid is dried to 12 hours at 120 ℃, 450 ℃ of roastings make required CuO/SiO for 4 hours afterwards
2catalyst I.
According to above-mentioned steps and condition, make catalyst I I, just in 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, be 100 grams, the filling ratio of catalyst I and catalyst I I is 1: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take dimethyl oxalate as 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 by the composite bed reactor of catalyst I and catalyst I I is housed successively, react, its reaction result is: the transformation efficiency of dimethyl oxalate is 80%, and the selectivity of methyl glycolate is 86.4%.
[embodiment 2]
The copper oxide catalyst I making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 40 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 0.5: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take dimethyl oxalate as 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 by the composite bed reactor of catalyst I and catalyst I I is 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]
The copper oxide catalyst I making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 45 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 0.3: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take dimethyl oxalate as 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 by the composite bed reactor of catalyst I and catalyst I I is 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]
The copper oxide catalyst I making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 50 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 0.8: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take dimethyl oxalate as 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 by the composite bed reactor of catalyst I and catalyst I I is 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 making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 20 parts, simultaneously, the oxide compound that also contains barium, its oxide compound of take 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 1.5: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take oxalic acid diethyl ester as 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 by the composite bed reactor of catalyst I and catalyst I I is 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]
The copper oxide catalyst I making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 30 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 3: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take oxalic acid diethyl ester as 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 by the composite bed reactor of catalyst I and catalyst I I is 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]
The copper oxide catalyst I making according to each Step By Condition of [embodiment 1] and copper oxide catalyst I I, wherein, for copper oxide catalyst I, take catalyst weight umber copper oxide as 25 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
According to catalyst I and catalyst I I gross weight, be 100 grams, the filling ratio of catalyst I and catalyst I I is 4: 1, packs successively catalyst I I and catalyst I (entry position) in reactor into.Take dimethyl oxalate as 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 by the composite bed reactor of catalyst I and catalyst I I is 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 example 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 (4)
1. a method for synthesizing alcohol acid esters, take barkite as raw material, in temperature of reaction, is 100～210 ℃, 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 with the composite bed reactor of copper oxide catalyst I I by copper oxide catalyst I is housed successively, generates the reaction effluent containing ethyl glycolate;
Wherein, in 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 the 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;
Copper oxide catalyst I, take catalyst weight umber copper oxide as 5～60 parts; 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 the oxide compound of the copper of copper oxide catalyst I I.
2. the method for synthesizing alcohol acid esters according to claim 1, is characterized in that 130～200 ℃ of temperature of reaction, and 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. the method for synthesizing alcohol acid esters according to claim 2, is characterized in that 140～200 ℃ of temperature of reaction, and weight space velocity is 0.4～3 hour
-1, hydrogen/ester mol ratio is 30～70: 1, reaction pressure is 2～4.0MPa.
4. the method for synthesizing alcohol acid esters according to claim 1, is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045233.XA CN102649743B (en) | 2011-02-25 | 2011-02-25 | Method for synthesizing glycollic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045233.XA CN102649743B (en) | 2011-02-25 | 2011-02-25 | Method for synthesizing glycollic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102649743A CN102649743A (en) | 2012-08-29 |
| CN102649743B true CN102649743B (en) | 2014-10-15 |
Family
ID=46691873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110045233.XA Active CN102649743B (en) | 2011-02-25 | 2011-02-25 | Method for synthesizing glycollic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649743B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649743A (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549443B (en) | polyformaldehyde dimethyl ether catalyst and application thereof | |
| CN102558106B (en) | Method for preparing 2-methyltetrahydrofuran from waste biomass | |
| CN101544539B (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN104725229B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN103113187B (en) | By the method for acetic acid ethanol co-production ethyl acetate | |
| CN104043455A (en) | Preparation method of catalyst for preparation of glycol by oxalate hydrogenation | |
| CN101768142B (en) | Method for catalysis-synthesizing 2,5-dicarbaldehyde by carbohydrate | |
| CN104926657B (en) | The method of oxalate gas phase hydrogenation synthesizing alcohol acid esters | |
| CN102649742B (en) | Method for increasing selectivity of glycollic acid ester | |
| CN104725230A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN102649743B (en) | Method for synthesizing glycollic acid ester | |
| CN102372604B (en) | Method for preparing 1, 6-hexanediol by hydrogenating 1, 6-dimethyl adipate | |
| CN105363438A (en) | Catalyst for synthesizing glycolic acid ester and preparation method and application of catalyst | |
| CN102649062A (en) | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation | |
| WO2015096009A1 (en) | Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate | |
| CN103613483A (en) | Application of layered loading catalyst in preparation of lower alcohol by using synthesis gas | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN102649057B (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN104707646A (en) | Catalyst for toluene preparation through oxidative dehydrogenation of dimethyl ether, preparation method and applications thereof | |
| CN102649072B (en) | Fluidized bed catalyst of glycolate catalyzed from oxalic ester | |
| CN102649744B (en) | Production method for glycolic acid ester | |
| CN103420791A (en) | Method for ethanol preparation through synthesis gas hydrogenation | |
| CN102649747B (en) | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction | |
| CN102219679A (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102649745B (en) | Method for preparing glycolate through oxalate gas phase hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |