CN102649686A - Method for synthesizing ethylene glycol - Google Patents
Method for synthesizing ethylene glycol Download PDFInfo
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- CN102649686A CN102649686A CN2011100452363A CN201110045236A CN102649686A CN 102649686 A CN102649686 A CN 102649686A CN 2011100452363 A CN2011100452363 A CN 2011100452363A CN 201110045236 A CN201110045236 A CN 201110045236A CN 102649686 A CN102649686 A CN 102649686A
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- terepthaloyl moietie
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for synthesizing ethylene glycol, and mainly solves the technical problem in the prior art that the selectivity of ethylene glycol is low. Through the adoption of the technical scheme that oxalic ester and hydrogen are taken as raw materials, the method comprises the following steps: (a) the raw materials enter into a reactor I at first to be in contact reaction with a catalyst I to generate a first effluent containing methyl glycolate/ethyl glycolate; (b) the first effluent containing methyl glycolate/ethyl glycolate enters into a reactor II to be in contact reaction with a catalyst II to generate a second effluent containing ethylene glycol, wherein the reactor I is a thermal-insulation fixed bed reactor, the reactor II is a tubular reactor, the catalyst I adopts Cu2+ as a main active component, and the catalyst II adopts Cu+ and CuO as main active components. Therefore, the invention solves the problem well, and can be used in the industrial production of increasing the yield of ethylene glycol.
Description
Technical field
The present invention relates to a kind of terepthaloyl moietie synthetic method, particularly carry out terepthaloyl moietie synthetic method about dimethyl oxalate hydrogenation or oxalic acid diethyl ester hydrogenation.
Background technology
Terepthaloyl moietie (EG) is a kind of important Organic Chemicals; Be mainly used in to produce and gather vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc.; Can be used for industries such as coating, soup, brake fluid and printing ink in addition; Solvent and medium as ammonium pertorate are used to produce special solvent glycol ether etc., and purposes very extensively.
At present, China has surpassed the U.S. becomes the big terepthaloyl moietie consumption of the first in the world big country, and domestic apparent consumption average annual growth rate reached 17.4% in 2001～2006 years.Though China's terepthaloyl moietie throughput and increase of production are very fast,, all need a large amount of imports every year, and import volume is growing trend year by year because the powerful development of industry such as polyester still can not be satisfied the growing market requirement.
Current, the suitability for industrialized production of domestic and international large-scale terepthaloyl moietie all adopts the oxyethane direct hydration, i.e. the legal operational path of pressurized water, and production technology is monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC three companies basically.In addition, the research-and-development activity of the new synthetic technology of terepthaloyl moietie is also making progress always.Developed catalyzing epoxyethane hydration legal system terepthaloyl moietie production technology in succession like Shell company, UCC company, Moscow Mendelyeev chemical engineering institute, Oil of Shanghai Petrochemical Company institute etc.; Companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system terepthaloyl moietie production technology in succession; Companies such as Dow chemistry have developed EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
For reaction product water cut height, follow-up equipment (vaporizer) long flow path of direct hydration method, equipment is big, energy consumption is high, the process total recovery has only about 70%, directly influences the production cost of EG.Direct hydration method is compared with catalytic hydration and has been reduced the water ratio significantly, has obtained higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalytic hydration system EG replacement on-catalytic hydrating process is trend of the times so.No matter the technology that NSC 11801 (EC) legal system is equipped with EG aspect EO transformation efficiency, EG selectivity, still all has bigger advantage than EO direct hydration method aspect raw material, the energy expenditure, is a kind of method that maintains the leading position.EG and DMC co-production technology can make full use of the CO of oxidation of ethylene by-product
2Resource in existing EO production equipment, only needs to increase the reactions step of producing EC and just can produce two kinds of very value products, and is very attractive.
But the drawback of aforesaid method is to need the consumption of ethylene resource; And mainly lean on traditional petroleum resources refining for present ethene; And under the situation of following one section global oil price in period high-order operation for a long time; Replace oil production terepthaloyl moietie (non-petroleum path is the CO route again) with aboundresources, low-cost Sweet natural gas or coal, can possess the advantage of competing mutually with traditional ethene route.Wherein, synthetic gas synthesizes the EG new technology, may produce great influence to the innovation of EG production technique.With the carbon monoxide is the feedstock production dimethyl oxalate, is a very attractive Coal Chemical Industry route with preparation of ethanediol by dimethyl oxalate hydrogenation then.Now both at home and abroad to being that the research of feedstock production dimethyl oxalate has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparation of ethanediol by dimethyl oxalate hydrogenation, especially effectively improve the selectivity of terepthaloyl moietie and improve also not well breakthrough on the catalyst stability how.
2010 27 volumes of document " spectrographic laboratory ", 2 phase 616-619 pages or leaves disclose the research of one piece of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen, and it has prepared Cu-B/ γ-Al through the chemical reduction sedimentation
2O
3, Cu-B/SiO
2Amorphous alloy catalyst, its evaluation result show, but this catalyzer barkite transformation efficiency is lower, and glycol selectivity is lower than 90%.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and the barkite transformation efficiency of this catalyzer and technology thereof is lower, and generally about 96%, the selectivity of terepthaloyl moietie is about about 92%.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of glycol selectivity that exists in the method for document in the past, and a kind of new terepthaloyl moietie synthetic method is provided.This method has the glycol selectivity advantages of higher.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of terepthaloyl moietie synthetic method is a raw material with barkite and hydrogen, comprises the steps:
A) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains ethyl glycolate;
B) the first strand of elute that contains ethyl glycolate gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie;
Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; Catalyst I is selected from Cu
2+Be main active ingredient, catalyst I I is selected from Cu
+And Cu
0It is main active ingredient.
The reaction conditions of reactor drum I is preferably in the technique scheme: 150～240 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～150: 1, reaction pressure is 1.5～4.0MPa; The reaction conditions of reactor drum I is 160～220 ℃ of temperature of reaction more preferably, and weight space velocity is 0.4～3 hour
-1, hydrogen/ester mol ratio is 30～100: 1, reaction pressure is 2～4.0MPa.The reaction conditions of reactor drum II is preferably: 160～260 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～130: 1, reaction pressure is 1.5～5.0MPa.The reaction conditions of reactor drum II is more preferably: 160～240 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 40～100: 1, reaction pressure is 1.5～4.0MPa.
The Cu of copper containing catalyst I in the technique scheme
2+Active ingredient is in catalyst weight umber Cu
2+Oxide compound be 0.1～40 part, more preferably scope is 2～40 parts; The Cu of catalyst I I
+And Cu
0Active ingredient is in catalyst weight umber Cu
+Oxide compound and Cu
0Total umber is 0.1～40 part, and more preferably scope is 3～40 parts; Its Cu
+Oxide compound and Cu
0Ratio is 0.01～100: 1, and more preferably scope is 0.01～50: 1.Barkite is preferably selected from dimethyl oxalate or oxalic acid diethyl ester, more preferably is selected from dimethyl oxalate.
As everyone knows; The process that the barkite hydrogenation generates terepthaloyl moietie is typical cascade reaction; The first step barkite at first hydrogenation generates ethyl glycolate, and the ethyl glycolate repeated hydrogenation makes terepthaloyl moietie then, and the reaction process in two steps is thermopositive reaction; In addition, terepthaloyl moietie can generate ethanol by further hydrogenation under proper condition.Research shows, the barkite hydrogenation generates in the process of terepthaloyl moietie, and the concentration of terepthaloyl moietie is by the outlet to reactor drum of the inlet of reactor drum in reactor drum, and the concentration general trend of terepthaloyl moietie raises gradually, and ethyl glycolate is the reduction gradually that raises earlier again.Because what the catalyzer of prior art mesoxalic acid ester through hydrogenation generation terepthaloyl moietie adopted is single catalyst system; The barkite hydrogenation is generated ethyl glycolate and ethyl glycolate repeated hydrogenation make that the reaction of terepthaloyl moietie is not significant to be selected to distinguish; This causes the ethyl glycolate that generates at the reactor inlet place to generate terepthaloyl moietie by faster reaction; This makes this terepthaloyl moietie in the probability increasing that generates side reaction in order through the further hydrogenation of the process of downstream catalyst, causes selectivity to reduce.The present inventor finds in research process, equally for copper class catalyzer, Cu
2+, Cu
+And Cu
0Effect be different, 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, and Cu
+And Cu
0Effect to make the reaction of terepthaloyl moietie for the ethyl glycolate repeated hydrogenation just more favourable.Technical scheme of the present invention is at first passed through Cu with the raw material barkite
2+Be the catalyst I of active ingredient, the high hydrogenation of selecting of raw material generates the logistics that is rich in ethyl glycolate, and Cu is passed through in the logistics that is rich in ethyl glycolate that will generate then again
+And Cu
0For the further hydrogenation of the catalyst I I of active ingredient makes terepthaloyl moietie.In addition; Discover that hydrogenation of oxalate for preparing gets the relative broad of temperature range of ethyl glycolate, and the ethyl glycolate hydrogenation makes the temperature range relative narrower of the reaction of terepthaloyl moietie; Therefore through catalyst I being placed among the insulation fix bed reactor I or in the shell-and-tube reactor; And catalyst I I is placed into the advantage of giving full play to different catalysts among the shell-and-tube reactor II, and both guaranteed transformation efficiency, improved selectivity again.
Adopting technical scheme of the present invention, is raw material with barkite and hydrogen, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains ethyl glycolate; (b) the first strand of elute that contains ethyl glycolate gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; Catalyst I is selected from Cu
2+Be main active ingredient, catalyst I I is selected from Cu
+And Cu
0It is main active ingredient.The reaction conditions of reactor drum I is: 150～240 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～150: 1, reaction pressure is 1.5～4.0MPa; The reaction conditions of reactor drum II is: 160～260 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～130: 1, and reaction pressure is 1.5～5.0MPa, and its result is: the transformation efficiency of oxalate diester is greater than 99%, and the selectivity of terepthaloyl moietie can obtain better technical effect greater than 97%.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Dipping method according to routine makes catalyst I and catalyst I I, and wherein the carrier of catalyzer is a silicon oxide, and catalyst I is in catalyst I parts by weight Cu
2+Oxide compound be 30 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 25 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 0.5: 1.
With dimethyl oxalate and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains NSC 27786; (b) the first strand of elute that contains NSC 27786 gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 160 ℃ of temperature of reaction, weight space velocity are 0.8 hour
-1, hydrogen/ester mol ratio is 40: 1, reaction pressure is 1.8MPa; The reaction conditions of reactor drum II is: 185 ℃ of temperature of reaction, weight space velocity are 0.4 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is 2.5MPa, and its result is: the transformation efficiency of dimethyl oxalate is 99%, and the selectivity of terepthaloyl moietie is 96.7%.
[embodiment 2]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 20 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 30 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 60: 1.
With dimethyl oxalate and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains NSC 27786; (b) the first strand of elute that contains NSC 27786 gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 170 ℃ of temperature of reaction, weight space velocity are 2 hours
-1, hydrogen/ester mol ratio is 50: 1, reaction pressure is 2.5MPa; The reaction conditions of reactor drum II is: 200 ℃ of temperature of reaction, weight space velocity are 0.6 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is 3.5MPa, and its result is: the transformation efficiency of dimethyl oxalate is 99%, and the selectivity of terepthaloyl moietie is 97.5%.
[embodiment 3]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 35 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 28 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 30: 1.
With dimethyl oxalate and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains NSC 27786; (b) the first strand of elute that contains NSC 27786 gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 200 ℃ of temperature of reaction, weight space velocity are 3.5 hours
-1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 3.5MPa; The reaction conditions of reactor drum II is: 240 ℃ of temperature of reaction, weight space velocity are 3.0 hours
-1, hydrogen/ester mol ratio is 130: 1, and reaction pressure is 3.5MPa, and its result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 98.2%.
[embodiment 4]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 15 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 35 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 3: 1.
With dimethyl oxalate and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains NSC 27786; (b) the first strand of elute that contains NSC 27786 gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 220 ℃ of temperature of reaction, weight space velocity are 3.0 hours
-1, hydrogen/ester mol ratio is 140: 1, reaction pressure is 3.0MPa; The reaction conditions of reactor drum II is: 220 ℃ of temperature of reaction, weight space velocity are 2.0 hours
-1, hydrogen/ester mol ratio is 110: 1, and reaction pressure is 3.0MPa, and its result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 98.5%.
[embodiment 5]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 28 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 26 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 0.3: 1.
With dimethyl oxalate and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains NSC 27786; (b) the first strand of elute that contains NSC 27786 gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 160 ℃ of temperature of reaction, weight space velocity are 0.5 hour
-1, hydrogen/ester mol ratio is 60: 1, reaction pressure is 2.0MPa; The reaction conditions of reactor drum II is: 230 ℃ of temperature of reaction, weight space velocity are 1.0 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is 3.0MPa, and its result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 97.5%.
[embodiment 6]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 22 parts, also contain Zn
2+Oxide compound be 3 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 33 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 2: 1.
With oxalic acid diethyl ester and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains ethyl glycollate; (b) the first strand of elute that contains ethyl glycollate gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is a shell-and-tube reactor, and reactor drum II also is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 180 ℃ of temperature of reaction, weight space velocity are 1.5 hours
-1, hydrogen/ester mol ratio is 50: 1, reaction pressure is 2.0MPa; The reaction conditions of reactor drum II is: 200 ℃ of temperature of reaction, weight space velocity are 0.8 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is 3.0MPa, and its result is: the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of terepthaloyl moietie is 97.7%.
[embodiment 7]
According to catalyst I and catalyst I I that each Step By Condition of [embodiment 1] makes, just it is in catalyst I parts by weight Cu
2+Oxide compound be 18 parts; Catalyst I I is in the total umber Cu of catalyst I I weight
+Oxide compound and total umber of elemental copper be 16 parts, wherein, Cu
+Oxide compound and the parts by weight ratio of elemental copper be 0.8: 1.
With oxalic acid diethyl ester and hydrogen is raw material, comprises the steps: that (a) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains ethyl glycollate; (b) the first strand of elute that contains ethyl glycollate gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie; Wherein, reactor drum I is a shell-and-tube reactor, and reactor drum II also is a shell-and-tube reactor; The reaction conditions of reactor drum I is: 170 ℃ of temperature of reaction, weight space velocity are 2.0 hours
-1, hydrogen/ester mol ratio is 40: 1, reaction pressure is 2.5MPa; The reaction conditions of reactor drum II is: 210 ℃ of temperature of reaction, weight space velocity are 1.0 hours
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is 2.5MPa, and its result is: the transformation efficiency of oxalic acid diethyl ester is 99.5%, and the selectivity of terepthaloyl moietie is 96.1%.
[Comparative Examples 1]
According to [embodiment 1] identical reaction conditions and raw material, just catalyzer only adopts catalyst I I, and reactor drum II also adopts insulation fix bed reactor, and its reaction result is: the transformation efficiency of dimethyl oxalate is 99.1%, and the selectivity of terepthaloyl moietie is 89.2%.
[Comparative Examples 2]
According to [embodiment 6] identical reaction conditions and raw material, just catalyzer only adopts catalyst I I, and reactor drum II also adopts insulation fix bed reactor, and its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 99.2%, and the selectivity of terepthaloyl moietie is 90.3%.
Claims (6)
1. a terepthaloyl moietie synthetic method is a raw material with barkite and hydrogen, comprises the steps:
A) raw material at first gets into reactor drum I and catalyst I contact reacts, generates the first strand of elute that contains ethyl glycolate;
B) the first strand of elute that contains ethyl glycolate gets into reactor drum II, with catalyst I I contact reacts, generates the second strand of elute that contains terepthaloyl moietie;
Wherein, reactor drum I is an insulation fix bed reactor, and reactor drum II is a shell-and-tube reactor; Catalyst I is selected from Cu
2+Be main active ingredient, catalyst I I is selected from Cu
+And Cu
0It is main active ingredient.
2. according to the said terepthaloyl moietie synthetic of claim 1 method, it is characterized in that the reaction conditions of reactor drum I is: 150～240 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～150: 1, reaction pressure is 1.5～4.0MPa; The reaction conditions of reactor drum II is: 160～260 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 30～130: 1, reaction pressure is 1.5～5.0MPa.
3. according to the said terepthaloyl moietie synthetic of claim 2 method, it is characterized in that the reaction conditions of reactor drum I is: 160～220 ℃ of temperature of reaction, weight space velocity are 0.4～3 hour
-1, hydrogen/ester mol ratio is 30～100: 1, reaction pressure is 2～4.0MPa.The reaction conditions of reactor drum II is: 160～240 ℃ of temperature of reaction, weight space velocity are 0.3～4 hour
-1, hydrogen/ester mol ratio is 40～100: 1, reaction pressure is 1.5～4.0MPa.
4. according to the said terepthaloyl moietie synthetic of claim 1 method, it is characterized in that the Cu of copper containing catalyst I
2+Active ingredient is in catalyst weight umber Cu
2+Oxide compound be 0.1～40 part; The Cu of catalyst I I
+And Cu
0Active ingredient is in catalyst weight umber Cu
+Oxide compound and Cu
0Total umber is 0.1～40 part, its Cu
+Oxide compound and Cu
0Ratio is 0.01～100: 1.
5. according to the said terepthaloyl moietie synthetic of claim 4 method, it is characterized in that the Cu of copper containing catalyst I
2+Active ingredient is in catalyst weight umber Cu
2+Oxide compound be 2～40 parts; The Cu of catalyst I I
+And Cu
0Active ingredient is in catalyst weight umber Cu
+Oxide compound and Cu
0Total umber is 3～40 parts, its Cu
+Oxide compound and Cu
0Ratio is 0.01～50: 1.
6. according to the said terepthaloyl moietie synthetic of claim 1 method, it is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
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| CN102211978A (en) * | 2011-04-15 | 2011-10-12 | 上海浦景化工技术有限公司 | Method for synthesizing glycol by hydrogenation of dimethyl oxalate |
| CN102211978B (en) * | 2011-04-15 | 2014-01-08 | 上海浦景化工技术有限公司 | Method for synthesizing glycol by hydrogenation of dimethyl oxalate |
| CN106928021A (en) * | 2017-02-20 | 2017-07-07 | 宁波中科远东催化工程技术有限公司 | A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN106928021B (en) * | 2017-02-20 | 2020-04-24 | 宁波中科远东催化工程技术有限公司 | Method for preparing ethylene glycol by dimethyl oxalate hydrogenation |
| CN107082741A (en) * | 2017-06-16 | 2017-08-22 | 四川天科技股份有限公司 | A kind of method of oxalate deep hydrogenation catalytic reaction synthesizing glycol |
| CN107082741B (en) * | 2017-06-16 | 2021-01-26 | 西南化工研究设计院有限公司 | Method for synthesizing ethylene glycol through oxalate deep hydrogenation catalytic reaction |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
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