CN102649746A - Method for producing glycolic acid ester through adding hydrogen in oxalic ester - Google Patents
Method for producing glycolic acid ester through adding hydrogen in oxalic ester Download PDFInfo
- Publication number
- CN102649746A CN102649746A CN2011100471472A CN201110047147A CN102649746A CN 102649746 A CN102649746 A CN 102649746A CN 2011100471472 A CN2011100471472 A CN 2011100471472A CN 201110047147 A CN201110047147 A CN 201110047147A CN 102649746 A CN102649746 A CN 102649746A
- Authority
- CN
- China
- Prior art keywords
- parts
- barkite
- ester
- ethyl glycolate
- reaction
- 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.)
- Pending
Links
Abstract
The invention relates to a method for producing glycolic acid ester through adding hydrogen in oxalic ester, which mainly solves the technical problem in the prior art that the selectivity of the glycolic acid ester is low in a hydrogenated production. The invention adopts the technical scheme that under conditions that the reaction temperature is 100-250 DEG C, the weight space velocity is 0.2-5 h<-1>, the molar ratio of hydrogen to ester is (10-100):1, and the reaction pressure is 0-6.0 MPa, raw materials, namely the oxalic ester, are in contact with a catalyst to generate an effluence containing the glycolic acid ester, wherein the catalyst, in parts by weight, comprises 5-80 parts of active component, 0-40 parts of additive and 1-90 parts of carrier. Due to the adoption of the technical scheme, the problem is better solved, and the method can be used in the industrial production of glycolic acid ester.
Description
Technical field
The present invention relates to the method that a kind of barkite is produced ethyl glycolate through hydrogenation, particularly pass through the method that hydrogenation is produced ethyl glycolate about dimethyl oxalate or oxalic acid diethyl ester catalysis.
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.
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 hydrogenation products ethyl glycolate selectivity in the technology in the past, the method that provides a kind of new barkite to produce ethyl glycolate through hydrogenation.This method has the high advantage of hydrogenation products ethyl glycolate selectivity.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: the method that a kind of barkite is produced ethyl glycolate through hydrogenation is a raw material with the barkite, is 100～250 ℃ 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 0～6.0MPa condition, and raw material contacts with catalyzer, generates the elute that contains ethyl glycolate; Wherein catalyzer comprises 5～80 parts active constituent, 0～40 part auxiliary agent and 1～90 part carrier in parts by weight; Active ingredient is oxide compound or its mixture of copper, copper, and auxiliary agent is selected from least a metal or its oxide compound in zinc, lanthanum, barium, chromium, nickel or the iron, and carrier is selected from least a in aluminum oxide, silicon oxide, zirconium white or the molecular sieve.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 150～220 ℃, and the barkite weight space velocity is 0.3～3 hour
-1, hydrogen/ester mol ratio is 20～80: 1, the reaction pressure scope is 0.5～3.0MPa.Catalyzer is 30～70 parts in parts by weight active constituent preferable range, and the auxiliary agent preferable range is 8～30 parts, and the carrier preferable range is 3～40 parts; Carrier is selected from least a in aluminum oxide or the silicon oxide.Barkite is preferably selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
The method for preparing the said catalyzer of the inventive method comprises the steps:
(1) takes by weighing carrier according to aequum;
(2) halogenide, acetate, vitriol or the nitrate salt dissolving with metallic copper is mixed with the aqueous solution; The concentration of solution is 0.002～2.0mol/L; To in this solution, flood 8～20 hours through the carrier that step (1) makes, then, vacuum-drying got solids I in 2～8 hours;
(3) nitrate salt, halogenide, acetate or oxalate and the water with auxiliary agent is mixed with the aqueous solution; The total concn of the aqueous solution is 0.001～2.0mol/L; The solids that step (2) is made soaks in this aqueous solution after 1～10 hour and takes out; 90～120 ℃ of dryings 6～8 hours, and pulverize and obtain solids II;
(4) solids II is added an amount of field mountain valley with clumps of trees and bamboo powder and mix, add an amount of forming agent furnishing mashed prod again, be extruded into required cylinder or trifolium shape then.Made solids III in 4 hours through 100～120 ℃ of dryings, 300～450 ℃ of roastings.
(5) using flow is 20～60 ml/min. the hydrogen of gram catalyzer 150 ℃～400 ℃ reductase 12～10 hour, makes catalyzer of the present invention to solids III.
Adopting the catalyzer of the present invention's preparation, is raw material with the barkite, is 100～250 ℃ 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 0.5～6.0MPa condition, and the transformation efficiency of barkite can be greater than 80%, and the selectivity of ethyl glycolate can obtain better technical effect greater than 80%.
Through embodiment and Comparative Examples the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Take by weighing 100 gram silica supports.By 20 parts of Cu, 5 parts of Ba and 2 parts of Fe/ vector contgs preparation catalyzer, its step is following: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, silica support flood 20 hours in this solution after, vacuum-drying 6 hours must solids I.Choose nitrate of baryta and iron nitrate; Charge capacity according to barium and iron is mixed with steeping fluid, generates oxyhydroxide or oxide precipitation for preventing Hydrolysis Reactions of Metal-ions, in steeping fluid, adds a small amount of nitric acid; Make PH=4～6 of steeping fluid; Above-mentioned then solids I soaked in steeping fluid 12 hours, became solid through fully absorbing after drying, and pulverized and obtain solids II; Solids II is added an amount of field mountain valley with clumps of trees and bamboo powder mix, add an amount of forming agent furnishing mashed prod again, be extruded into cylindric solid then, made solids III in 6 hours through 120 ℃ of dryings, 430 ℃ of roastings; Using flow is 30 ml/min. the hydrogen of gram catalyzer 300 ℃ of reduction 8 hours, makes catalyst A of the present invention to solids III.
With the oxalic acid diethyl ester is raw material, is 200 ℃ in temperature of reaction, and weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 0.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 83.8%, and the selectivity of ethyl glycollate is 83.1%.
[embodiment 2]
According to each step and the condition of embodiment 1, just catalyzer consists of 21 parts of Cu, 4 parts of Cu
2O and 0.5 part of Zn/SiO
2, be raw material with the dimethyl oxalate, be 170 ℃ in temperature of reaction, weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 2.8MPa, and raw material contacts with catalyzer, and reaction generates the elute that contains NSC 27786, and its reaction result is: the transformation efficiency of dimethyl oxalate is 84.7%, and the selectivity of ethyl glycolate is 85.1%.
[embodiment 3]
According to each step and the condition of embodiment 1, just catalyzer consists of 15 parts of Cu, 10 parts of Cr, 1 part of Cu
2O/Al
2O
3, be raw material with the dimethyl oxalate, be 150 ℃ 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 condition of 1.0MPa, and the transformation efficiency of dimethyl oxalate is 78.3%, and the selectivity of NSC 27786 is 76.2%.
[embodiment 4]
According to each step and the condition of embodiment 1, just catalyzer consists of 38 parts of Cu, 2 parts of Fe and 8 parts of Cu
2O/SiO
2, be raw material with the oxalic acid diethyl ester, be 200 ℃ in temperature of reaction, weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 0.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 87.1%, and the selectivity of ethyl glycollate is 86.1%.
[embodiment 5]
According to each step and the condition of embodiment 1, just catalyzer consists of 15 parts of Cu, 0.8 part of Cu
2O and 10 parts of Zn/ZSM-5 (silica alumina ratio is 500: 1) are raw material with the dimethyl oxalate, are 220 ℃ in temperature of reaction, and weight space velocity is 5 hours
-1, hydrogen/ester mol ratio is 20: 1, and reaction pressure is under the condition of 4.8MPa, and the transformation efficiency of dimethyl oxalate is 92.5%, and the selectivity of NSC 27786 is 79.5%.
[embodiment 6]
According to each step and the condition of embodiment 1, just catalyzer consists of 28 parts of Cu, 0.01 part of Ba and 3 parts of Cu
2O/Al
2O
3, be raw material with the dimethyl oxalate, be 190 ℃ in temperature of reaction, weight space velocity is 1.0 hours
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.0MPa, and the transformation efficiency of dimethyl oxalate is 86.1%, and the selectivity of NSC 27786 is 84.3%.
[embodiment 7]
According to each step and the condition of embodiment 1, just catalyzer consists of 20 parts of Cu, 3 parts of Cu
2O and 3%Cr/Al
2O
3, be raw material with the dimethyl oxalate, be 170 ℃ 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 condition of 0.8MPa, and the transformation efficiency of dimethyl oxalate is 88.6%, and the selectivity of NSC 27786 is 82.5%.
[comparative example 1]
Adopt the catalyzer of embodiment 7, each step and condition according to embodiment 7 just adopt fixed-bed reactor, and its reaction result does, the transformation efficiency of dimethyl oxalate is 80.3%, and the selectivity of NSC 27786 is 72.2%.
Claims (4)
1. the method that barkite is produced ethyl glycolate through hydrogenation is a raw material with the barkite, is 100～250 ℃ 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 0～6.0MPa condition, and raw material contacts with catalyzer, generates the elute that contains ethyl glycolate; Wherein catalyzer comprises 5～80 parts active constituent, 0～40 part auxiliary agent and 1～90 part carrier in parts by weight; Active ingredient is oxide compound or its mixture of copper, copper, and auxiliary agent is selected from least a metal or its oxide compound in zinc, lanthanum, barium, chromium, nickel or the iron, and carrier is selected from least a in aluminum oxide, silicon oxide, zirconium white or the molecular sieve.
2. produce the method for ethyl glycolate through hydrogenation according to the said barkite of claim 1; It is characterized in that temperature of reaction is 150～220 ℃; The barkite weight space velocity is 0.3～3 hour-1, and hydrogen/ester mol ratio is 20～80: 1, and the reaction pressure scope is 0.5～3.0MPa.
3. the method for producing ethyl glycolate according to the said barkite of claim 1 through hydrogenation is characterized in that catalyzer in 30～70 parts of parts by weight active constituents, 8～30 parts of auxiliary agents, 3～40 parts in carrier; Carrier is selected from least a in aluminum oxide or the silicon oxide.
4. the method for producing ethyl glycolate according to the said barkite of claim 1 through hydrogenation is characterized in that barkite is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100471472A CN102649746A (en) | 2011-02-25 | 2011-02-25 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100471472A CN102649746A (en) | 2011-02-25 | 2011-02-25 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102649746A true CN102649746A (en) | 2012-08-29 |
Family
ID=46691876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100471472A Pending CN102649746A (en) | 2011-02-25 | 2011-02-25 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649746A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105622418A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method and catalyst for hydrogenating oxalate to produce methyl glycolate |
| CN108499564A (en) * | 2018-03-13 | 2018-09-07 | 浙江师范大学 | Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application |
| CN111569876A (en) * | 2020-04-29 | 2020-08-25 | 厦门大学 | Hydrogenation catalyst, preparation method and application thereof |
Citations (5)
| 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 |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| 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 |
| CN101733108A (en) * | 2008-11-27 | 2010-06-16 | 上海焦化有限公司 | Catalyst for hydrogenation, preparation method thereof and use thereof |
| 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 CN2011100471472A patent/CN102649746A/en active Pending
Patent Citations (5)
| 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 |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101733108A (en) * | 2008-11-27 | 2010-06-16 | 上海焦化有限公司 | Catalyst for hydrogenation, preparation method thereof and use thereof |
| 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105622418A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method and catalyst for hydrogenating oxalate to produce methyl glycolate |
| CN108499564A (en) * | 2018-03-13 | 2018-09-07 | 浙江师范大学 | Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application |
| CN108499564B (en) * | 2018-03-13 | 2020-11-03 | 浙江师范大学 | Catalyst in synthesis process of methyl glycolate and preparation method and application thereof |
| CN111569876A (en) * | 2020-04-29 | 2020-08-25 | 厦门大学 | Hydrogenation catalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN102872878B (en) | Catalyst for preparing ethanol from acetic ester hydrogenation, preparation method and application thereof | |
| CN102558106B (en) | Method for preparing 2-methyltetrahydrofuran from waste biomass | |
| CN102649062A (en) | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation | |
| CN108997274A (en) | A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN101428229B (en) | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof | |
| CN101947451A (en) | Cobalt-based catalyst and preparation method and application thereof | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN102649742B (en) | Method for increasing selectivity of glycollic acid ester | |
| CN110368949A (en) | A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application | |
| CN102690170B (en) | Method for preparing ethanol by acetic acid gas phase hydrogenation | |
| CN111036198A (en) | Double-shell core-shell structure metal catalyst and preparation method thereof | |
| CN103664543B (en) | The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde | |
| CN101653729B (en) | Catalyst used for preparing lower alcohol by synthesis gas, preparation method and application thereof | |
| CN102649743B (en) | Method for synthesizing glycollic acid ester | |
| CN101934232B (en) | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas | |
| CN102649072B (en) | Fluidized bed catalyst of glycolate catalyzed from oxalic ester | |
| CN104588022B (en) | Reduction method of Fischer-Tropsch synthesis catalyst | |
| CN102557872A (en) | Method for preparing propanediol through one-step glycerol hydrogenolysis | |
| CN102649057A (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN112275304B (en) | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof | |
| CN113731413A (en) | MOFs (metal organic frameworks) limited-area metal catalyst and preparation method and application thereof | |
| CN103709018A (en) | Method for preparing guaiacol | |
| CN102649744A (en) | Production method for glycolic acid ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120829 |