CN102649062A - Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation - Google Patents
Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation Download PDFInfo
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- CN102649062A CN102649062A CN2011100471491A CN201110047149A CN102649062A CN 102649062 A CN102649062 A CN 102649062A CN 2011100471491 A CN2011100471491 A CN 2011100471491A CN 201110047149 A CN201110047149 A CN 201110047149A CN 102649062 A CN102649062 A CN 102649062A
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Abstract
The invention relates to a catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation, which mainly solves the technical problem of low selectivity of hydroxyacetic acid ester in hydrogenated products in the prior art. The catalyst comprises the following components as per parts by weight: 5 to 80 parts of active component, 0 to 40 parts of assistant and 1 t0 30 parts of carriers, wherein the active component is copper, oxide of copper of copper mixture; the assistant is at least one of zinc, lanthanum, barium, nickel or iron or oxide of zinc, lanthanum, barium, nickel or iron; and the carrier is a complex carrier chosen from alumina and silicon oxide, and the weight ratio of the alumina and silicon oxide is 0.01 to 30:1. The catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation can solve the problem well, and can be used for industrial production of hydroxyacetic acid ester.
Description
Technical field
The present invention relates to the catalyst of a kind of oxalate, particularly pass through the catalyst that hydrogenation is produced ethyl glycolate about dimethyl oxalate or diethy-aceto oxalate catalysis through hydrogenation production ethyl glycolate.
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, oxidation reaction etc. can take place, become a kind of important chemical material.Ethyl glycolate is the fine solvent of many celluloses, resin, rubber.Its downstream product glycolic, glycine, dimethyl malenate and glyoxalic acid etc. also are with a wide range of applications.
At present, the domestic production technology that does not have ripe eco-friendly ethyl glycolate.Still adopt chloroactic acid method production, its technology is that monoxone is mixed, stirs with soda lye.On boiling water bath, heat, reduction vaporization, filtering sodium chloride, in oil bath, heat paste liquid, add the methyl alcohol and the concentrated sulfuric acid afterwards, reflux methyl glycollate, with sodium carbonate 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 process route.Opened up the new important channel that C-1 chemistry is produced oxalate by CO and nitrites synthesis of oxalic ester by gaseous catalysis.And then under catalytic action, the oxalate hydrogenation is come the ethanol production acid esters.Reported the new development of ethyl glycolate both at home and abroad successively.As in Deutsche Bundespatent 45603, use the Cr/Cu catalyst that makes by cupric and trivalent chromium that hydrogenation of oxalate for preparing is got the hexanol acid esters.The Cr/Cu catalyst is the catalyst 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 basis of this catalyst, 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 activating catalyst, is raw material again with the glyoxal water solution; Activating catalyst carries out esterification with C4-C8 unit alcohol under nitrogen atmosphere, from product, collect the target 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 natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental pressure, is unusual important field of research.With the carbon monoxide is the feedstock production oxalate, 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, provides a kind of new oxalate to produce the catalyst of ethyl glycolate through hydrogenation.This catalyst 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: a kind of oxalate comprises active component, auxiliary agent and carrier through the catalyst of hydrogenation production ethyl glycolate, and is following in the parts by weight component:
(a) 5～80 parts active component;
(b) greater than 0～40 part auxiliary agent;
(c) 1～90 part carrier;
Wherein active component is oxide or its mixture of copper, copper; Auxiliary agent is selected from least a metal or its oxide in zinc, lanthanum, barium, chromium, nickel or the iron; Carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 0.01～30: 1.
Be 30～70 parts of active components in parts by weight catalytic component preferable range in the technique scheme, 8～30 parts of auxiliary agents, 3～40 parts in carrier.Carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio preferable range of aluminium oxide and silica is 0.01～20: 1.
Technique scheme medium-height grass acid esters is selected from dimethyl oxalate, diethy-aceto oxalate or its mixture.The preferred reaction conditions of producing the catalyst of ethyl glycolate is: 100～250 ℃ of reaction temperatures, weight space velocity 0.2～5 hour
-1, hydrogen/ester mol ratio is 10～100: 1, reaction pressure is 0.5～6.0MPa.
The method for preparing catalyst according to the invention comprises the steps:
(1) takes by weighing carrier according to aequum;
(2) halide, acetate, sulfate or the nitrate 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, halide, acetate or oxalates and the water with auxiliary agent is mixed with the aqueous solution; The total concentration 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 pastel again, be extruded into required cylinder or clover 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 catalyst 150 ℃～400 ℃ reductase 12～10 hour, makes catalyst of the present invention to solids III.
Adopting the catalyst of the present invention's preparation, is raw material with the oxalate, is 100～250 ℃ in reaction temperature, 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 conversion ratio of oxalate can be greater than being 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.
The specific embodiment
[embodiment 1]
The weight ratio that takes by weighing aluminium oxide 100 gram aluminium oxide and silica is 4: 1 a composite carrier carrier.By 20 parts of Cu, 5 parts of Ba and 2 parts of Fe content preparation catalyst, its step is following: choose copper nitrate, be mixed with maceration extract according to the Cu load capacity, silica support flood 20 hours in this solution after, vacuum drying 6 hours must solids I.Choose barium nitrate and ferric nitrate; Load capacity according to barium and iron is mixed with maceration extract, generates hydroxide or oxide precipitation for preventing Hydrolysis Reactions of Metal-ions, in maceration extract, adds a small amount of nitric acid; Make PH=4～6 of maceration extract; Above-mentioned then solids I soaked in maceration extract 12 hours, after fully absorbing, was dried to solid, 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 pastel 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 catalyst 300 ℃ of reduction 8 hours, makes catalyst required for the present invention to solids III.
With the diethy-aceto oxalate is raw material, is 200 ℃ in reaction temperature, 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 conversion ratio of diethy-aceto oxalate is 82%, and the selectivity of ethyl glycolate is 81.8%.
[embodiment 2]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 1: 1 a composite carrier, catalyst consist of 21 parts of Cu, 4 parts of Cu
2O, 0.5 part of Zn/SiO
2, be raw material with the dimethyl oxalate, be 170 ℃ in reaction temperature, 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 catalyst, and reaction generates the effluent that contains methyl glycollate, and its reaction result is: the conversion ratio of dimethyl oxalate is 82%, and the selectivity of ethyl glycolate is 83%.
[embodiment 3]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 0.1: 1 a composite carrier, and 15 parts of Cu, 10 parts of Cr, 1 part of Cu are urged in consisting of of catalyst
2O is a raw material with the dimethyl oxalate, is 150 ℃ in reaction temperature, and 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 conversion ratio of dimethyl oxalate is 75%, and the selectivity of methyl glycollate is 73%.
[embodiment 4]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 0.2: 1 a composite carrier, catalyst consist of 38 parts of Cu, 2 parts of Fe and 8 parts of Cu
2O is a raw material with the diethy-aceto oxalate, is 200 ℃ in reaction temperature, 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 conversion ratio of diethy-aceto oxalate is 82%, and the selectivity of ethyl glycolate is 81.8%.
[embodiment 5]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 2: 1 a composite carrier, catalyst consist of 15 parts of Cu, 0.8 part of Cu
2O and 10 parts of Zn are raw material with the dimethyl oxalate, are 220 ℃ in reaction temperature, 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 conversion ratio of dimethyl oxalate is 98.5%, and the selectivity of methyl glycollate is 78.3%.
[embodiment 6]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 0.05: 1 a composite carrier, catalyst consist of 28 parts of Cu, 0.01 part of Ba and 3 parts of Cu
2O is a raw material with the dimethyl oxalate, is 190 ℃ in reaction temperature, and 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 conversion ratio of dimethyl oxalate is 84%, and the selectivity of methyl glycollate is 80.1%.
[embodiment 7]
According to each step and the condition of embodiment 1, just the carrier of catalyst is that the weight ratio of aluminium oxide and silica is 2: 1 a composite carrier, catalyst consist of 20 parts of Cu, 3 parts of Cu
2O and 3 parts of Cr are raw material with the dimethyl oxalate, are 170 ℃ in reaction temperature, and 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 conversion ratio of dimethyl oxalate is 86%, and the selectivity of methyl glycollate is 79.9%.
[comparative example 1]
Employing is according to Cu-Ag/SiO among the document CN2007100613901.8
2(W) catalyst, according to each step and its reaction result of condition of embodiment 6 do, the conversion ratio of dimethyl oxalate is 82%, the selectivity of methyl glycollate is 73%.
Claims (4)
1. an oxalate passes through the catalyst that hydrogenation is produced ethyl glycolate, comprises active component, auxiliary agent and carrier, and is following in the parts by weight component:
(a) 5～80 parts active component;
(b) greater than 0～40 part auxiliary agent;
(c) 1～90 part carrier;
Wherein active component is oxide or its mixture of copper, copper; Auxiliary agent is selected from least a metal or its oxide in zinc, lanthanum, barium, chromium, nickel or the iron; Carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 0.01～30: 1.
2. according to the catalyst of the said oxalate of claim 1, it is characterized in that in 30～70 parts of parts by weight active components 8～30 parts of auxiliary agents, 3～40 parts in carrier through hydrogenation production ethyl glycolate; Carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 0.01～20: 1.
3. according to the catalyst of the said oxalate of claim 1, it is characterized in that oxalate is selected from dimethyl oxalate, diethy-aceto oxalate or its mixture through hydrogenation production ethyl glycolate.
4. produce the catalyst of ethyl glycolate according to the said oxalate of claim 1 through hydrogenation, the reaction temperature that it is characterized in that producing the catalyst of ethyl glycolate is 100～250 ℃, and weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 10～100: 1, reaction pressure is 0.5～6.0MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043457A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Catalyst and method for preparation of glycol by oxalate hydrogenation |
| 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 |
| CN109201059A (en) * | 2018-08-28 | 2019-01-15 | 华东师范大学 | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application |
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
| CN112206775A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and application of prepared catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
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- 2011-02-25 CN CN2011100471491A patent/CN102649062A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043457A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Catalyst and method for preparation of glycol by oxalate hydrogenation |
| 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 |
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
| CN109201059A (en) * | 2018-08-28 | 2019-01-15 | 华东师范大学 | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application |
| CN112206775A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and application of prepared catalyst |
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Application publication date: 20120829 |