CN102649747A - Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction - Google Patents
Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction Download PDFInfo
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Abstract
The invention relates to a method for producing glycolic acid ester by oxalic ester through a fluidized bed reaction, which mainly solves the technical problem in the prior art that the selectivity of the glycolic acid ester is low in a hydrogenation production. According to the invention, a fluidized bed reactor is utilized, and the technical scheme adopted is 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 0.5-6.0 MPa, raw materials, namely the oxalic ester, are in contact with a fluidized bed catalyst to generate an effluence containing the glycolic acid ester; and in the parts by the overall weight of the fluidized bed catalyst, the catalyst comprises 5-80 parts of active component which are copper and copper oxide, 10-90 parts of carries which are one or more than one of silicon oxide, a molecular sieve or aluminum oxide, and 0.01-30 parts of additive which is cerium and niobium metal element or oxide thereof. According to the invention, the problem is better solved, and the method is suitable for the industrial production of the glycolic acid ester.
Description
Technical field
The present invention relates to the method for a kind of barkite, particularly pass through the method that fluidized-bed reaction generates ethyl glycolate about dimethyl oxalate or oxalic acid diethyl ester through fluidized-bed reaction generation 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 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 problem of hydrogenation products ethyl glycolate selectivity that in the past exists in the technology.Provide a kind of new barkite to generate the method for ethyl glycolate through fluidized-bed reaction.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: a kind of barkite adopts fluidized-bed reactor through the method for fluidized-bed reaction generation ethyl glycolate, is raw material with the barkite; In temperature of reaction is 100～250 ℃, 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 raw material contacts with fluid catalyst, generates the elute that contains ethyl glycolate; In fluid catalyst gross weight umber; Catalyzer comprises that 5～80 parts copper and oxide compound thereof are at least aly in active ingredient, 10～90 parts silicon oxide, molecular sieve or the aluminum oxide to be carrier, and 0.01～30 part cerium and niobium metal element or its oxide compound are auxiliary agent;
Wherein, the average specific surface area of fluid catalyst carrier is 50 meters squared per gram～800 meters squared per gram, and the average particulate diameter of catalyzer is 20～300 microns.
The reaction conditions of fluidized-bed reactor 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.Barkite is preferably selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
In the technique scheme in the total catalyst weight umber; Copper and the oxide compound thereof that preferably includes 10～60 parts is at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part cerium and niobium metal element or its oxide compound are auxiliary agent.The average specific surface area preferable range of carrier is 50 meters squared per gram～600 meters squared per gram; The average particulate diameter preferable range of catalyzer is 50～200 microns.Total catalyst weight umber meter, the auxiliary agent umber of cerium metal element and its oxide compound more preferably scope is 0.01～20 part; The auxiliary agent umber of praseodymium metallic element and its oxide compound more preferably scope is 0.01～20 part.
The Preparation of catalysts method of the inventive method comprises the steps: that (a) disposes the mixed nitrate solution and the sodium carbonate solution of certain density copper, cerium and niobium; (b) above-mentioned solution constantly stirs in the precipitation process 60～80 ℃ of following co-precipitation, PH=5～8 when deposition stops; (C) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+The back adds the sticker making beating; (d) with the press spray moisture eliminator by the requirement granularity carry out spray shaping, granules of catalyst diameter average out to 20-300 micron is preferably the 50-200 micron, particle is ball-type; (e) 120 ℃ of dryings are 4～10 hours, 300～500 ℃ of following roastings 2～6 hours.
The catalyzer of the inventive method has following characteristics:
1. catalyzer adopts spray drying forming, thereby obtains to be suitable for the microspheric catalyst particle that fluidized-bed uses.
2. the introducing of cerium and niobium auxiliary agent makes catalyzer show catalytic performance preferably in the catalyzer.
Adopting the fluid catalyst of the present invention and the present invention preparation, adopt fluidized-bed reactor, is being 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 being 80%, and the selectivity of ethyl glycolate obtains 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]
By the content preparation catalyzer of the silicon oxide of 20 parts of Cu, 5 parts of Ce, 2 parts of Nd and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 70 ℃ of following co-precipitation, PH=6 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding silica support (specific surface area 150 meters squared per gram) and concentration are 10% silica sol binder making beating; (d) carry out spray shaping with the press spray moisture eliminator, 100 microns of control catalyst particle diameter average out to, particle is ball-type; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make fluid catalyst A.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 170 ℃ in temperature of reaction, and 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 A, and reaction generates the elute that contains NSC 27786, and its reaction result is: the transformation efficiency of dimethyl oxalate is 82%, and the selectivity of ethyl glycolate is 83%.
[embodiment 2]
Each step and condition according to embodiment 1; Control catalyst particle diameter average out to is 150 microns when being shaping of catalyst; Particle is ball-type, and its carrier average specific surface area is 280 meters squared per gram, and the catalyst B that makes thus is 30 parts of Cu, 10 parts of Ce, 1 part of Nd and surplus silicon oxide.Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 150 ℃ in temperature of reaction, 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 transformation efficiency of dimethyl oxalate is 75%, and the selectivity of NSC 27786 is 73%.
[embodiment 3]
By 40 parts of Cu, 3 parts of Ce, 15 parts of Nd and the silicon oxide of surplus and the content preparation catalyzer of aluminum oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, PH=7 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding alumina supporter (specific surface area 300 meters squared per gram) and concentration are 15% silica sol binder making beating; (d) carry out spray shaping with the press spray moisture eliminator, 150 microns of control catalyst particle diameter average out to, particle is ball-type; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make fluid catalyst C.
Adopting fluidized-bed reactor, is raw material with the oxalic acid diethyl ester, 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 82%, and the selectivity of ethyl glycollate is 81.8%.
[embodiment 4]
By 30 parts of Cu, 1 part of Ce, 8 parts of Nd and the silicon oxide of surplus and the content preparation catalyzer of aluminum oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, PH=7 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding alumina supporter (specific surface area 100 meters squared per gram) and concentration are 6% silica sol binder making beating; (d) carry out spray shaping with the press spray moisture eliminator, 120 microns of control catalyst particle diameter average out to, particle is ball-type; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make fluid catalyst D.
Adopting fluidized-bed reactor, is raw material with the oxalic acid diethyl ester, is 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 oxalic acid diethyl ester is 98.5%, and the selectivity of ethyl glycollate is 78.3%.
[embodiment 5]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 45 parts of Cu, 8 parts of Ce, 2 parts of Nd and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, PH=5 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific surface area 450 meters squared per gram) making beating; (d) carry out spray shaping with the press spray moisture eliminator, 140 microns of control catalyst particle diameter average out to, particle is ball-type; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make fluid catalyst E.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 190 ℃ in temperature of reaction, 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 transformation efficiency of dimethyl oxalate is 84%, and the selectivity of NSC 27786 is 80.1%.
[embodiment 6]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 25 parts of Cu, 0.8 part of Ce, 4 parts of Nd and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, PH=5 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific surface area 400 meters squared per gram) making beating; (d) carry out spray shaping with the press spray moisture eliminator, 140 microns of control catalyst particle diameter average out to, particle is ball-type; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make fluid catalyst.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 170 ℃ in temperature of reaction, 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 transformation efficiency of dimethyl oxalate is 86%, and the selectivity of NSC 27786 is 79.9%.
[comparative example 1]
Employing is according to Cu-Ag/SiO among the document CN2007100613901.8
2(W) catalyzer, according to each step and its reaction result of condition of embodiment 6 do, the transformation efficiency of dimethyl oxalate is 82%, the selectivity of NSC 27786 is 73%.
Claims (6)
1. a barkite passes through the method that fluidized-bed reaction generates ethyl glycolate, adopts fluidized-bed reactor, 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 raw material contacts with fluid catalyst, generates the elute that contains ethyl glycolate; In fluid catalyst gross weight umber; Catalyzer comprises that 5～80 parts copper and oxide compound thereof are at least aly in active ingredient, 10～90 parts silicon oxide, molecular sieve or the aluminum oxide to be carrier, and 0.01～30 part cerium and niobium metal element or its oxide compound are auxiliary agent;
Wherein, the average specific surface area of fluid catalyst carrier is 50 meters squared per gram～800 meters squared per gram, and the average particulate diameter of catalyzer is 20～300 microns.
2. according to the method for the said barkite of claim 1 through fluidized-bed reaction generation ethyl glycolate, the temperature of reaction that it is characterized in that fluidized-bed reactor 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.
3. generate the method for ethyl glycolate through fluidized-bed reaction according to the said barkite of claim 1; It is characterized in that in the total catalyst weight umber; Copper and the oxide compound thereof that comprises 10～60 parts is at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part cerium and niobium metal element or its oxide compound are auxiliary agent.
4. according to the method for the said barkite of claim 3 through fluidized-bed reaction generation ethyl glycolate, the average specific surface area that it is characterized in that carrier is 50 meters squared per gram～600 meters squared per gram; The average particulate diameter of catalyzer is 50～200 microns.
5. according to the method for the said barkite of claim 4, it is characterized in that the auxiliary agent umber of cerium metal element and its oxide compound is 0.01～20 part in the total catalyst weight umber through fluidized-bed reaction generation ethyl glycolate; The auxiliary agent umber of niobium metal element and its oxide compound is 0.01～20 part.
6. according to the method for the said barkite of claim 1 through fluidized-bed reaction generation ethyl glycolate, barkite is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
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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 |
| CN1516619A (en) * | 2001-06-04 | 2004-07-28 | ��ʽ�����ձ���ý | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| 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 |
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2011
- 2011-02-25 CN CN201110047150.4A patent/CN102649747B/en active Active
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 |
| CN1516619A (en) * | 2001-06-04 | 2004-07-28 | ��ʽ�����ձ���ý | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| 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 |
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