CN102649705A - Ethylene glycol production method - Google Patents
Ethylene glycol production method Download PDFInfo
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- CN102649705A CN102649705A CN2011100471928A CN201110047192A CN102649705A CN 102649705 A CN102649705 A CN 102649705A CN 2011100471928 A CN2011100471928 A CN 2011100471928A CN 201110047192 A CN201110047192 A CN 201110047192A CN 102649705 A CN102649705 A CN 102649705A
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- fluidized
- bed reactor
- 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 an ethylene glycol production method, and mainly solves the technical problem in the prior art that ethylene glycol is low in selectivity. The method adopts oxalate as the raw material and at least one of the matters selected from water and C2-C5 alcohol as a terminator, and comprises the following steps: (a) the raw material enters to be in contact reaction with a catalyst from the bottom of a fluidized bed reactor to form an effluent I containing both ethylene glycol and catalyst; (b) the effluent I formed in the step (a) is in contact with the terminator at the bottom of a gas-solid quick separation area at the upper part of a transition zone of the fluidized bed reactor, so as to form an effluent II which is subjected to gas-solid separation after entering the gas-solid quick separation area at the upper part of the fluidized bed reactor, and then a solid catalyst enters an activator for activation; and (c) an activated catalyst from the activator returns to a dense-phase zone at the bottom of the fluidized bed reactor for continuous reaction. By adopting the technical scheme, the problem is better solved, and the method provided by the invention can be used for industrial increase production of ethylene glycol.
Description
Technical field
The present invention relates to a kind of working method of terepthaloyl moietie, particularly pass through the method that the fluidized-bed catalyzed reaction generates terepthaloyl moietie about dimethyl oxalate or oxalic acid diethyl ester catalysis.
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 the further investigation of more need of work with preparation of ethanediol by dimethyl oxalate hydrogenation, especially effectively improve on the selectivity of terepthaloyl moietie and also have more need of work research 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%.
The subject matter that above-mentioned document exists is that glycol selectivity is lower, remains further to improve and improve.
Summary of the invention
Technical problem to be solved by this invention is the low problem of glycol selectivity that in the past exists in the technology.A kind of working method of new terepthaloyl moietie is provided.This method has the high advantage of glycol 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 working method of terepthaloyl moietie is a raw material with the barkite, to be selected from water, C
2～C
5At least a in the alcohol is terminator, may further comprise the steps:
(a) raw material at first gets into from the fluidized-bed reactor bottom, in fluidized-bed reactor emulsion zone and zone of transition and catalyzer contact reacts, forms the elute I that contains ethene and catalyzer;
(b) the elute I from (a) step contacts with terminator in the bottom, gas-solid sharp separation district on fluidized-bed reactor zone of transition top; Form elute II; Elute II gets into the gas-solid sharp separation district on fluidized-bed reactor top after gas solid separation; Gas gets into follow-up workshop section to be separated, and solid catalyst gets into the activator activation;
(c) return the fluidized-bed reactor bottom dense from the deactivated catalyst of activator and proceed reaction.
In the technique scheme in the fluidized-bed reactor zone of transition of emulsion zone through the undergauge structure link to each other with gas-solid sharp separation district.The reaction conditions of fluidized-bed reactor is preferably: temperature of reaction is 170～270 ℃, and the barkite weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 40～200: 1, reaction pressure is 1.5～10MPa.The reaction conditions of fluidized-bed reactor is more preferably: temperature of reaction is 180～260 ℃, and the barkite weight space velocity is 0.3～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1, reaction pressure is 2.0～6.0MPa.The catalyzer preferred version is in the total catalyst 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 bismuth and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter preferable range of catalyzer is 20～300 microns.Catalyzer more preferably scheme in the total catalyst weight umber; Catalyzer comprises that 10～60 parts copper and oxide compound thereof are at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 30～200 microns.
The fluidized-bed reactor preferred version is selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor.Fluidized-bed reactor more preferably scheme is selected from fast fluidized bed.The weight ratio of raw material and terminator is 5～1000: 1, and the terminator feeding temperature is 10～200 ℃.
Adopt in the hydrogenation of oxalate for preparing ethylene glycol reaction process; Under raw material and the catalyzer Long contact time situation; Still can continue to transform, especially at the settling zone of hydrogenation of oxalate for preparing ethylene glycol fluidized-bed reactor, a large amount of unsegregated catalyzer can continue to react under the condition of high temperature; Cause the barkite rate of loss high, glycol selectivity is low.The present invention injects terminator through the zone, outlet position of leaving catalytic bed in catalyzer and reaction product; The lower terminator of temperature is contacted with pyroreaction mixture and catalyzer, can significantly reduce the temperature of reaction mixture and catalyzer, the rapid reduction of temperature; After making reaction mixture and catalyzer leave reaction zone; Side reaction is few, and it is little to continue the reaction odds, has reduced the rate of loss of raw material.On the other hand, reacted catalyzer can further improve the selectivity of terepthaloyl moietie after the hydrogen activation.
The present invention adopts fluidized-bed reactor to be used for the hydrogenation of oxalate for preparing ethylene glycol reaction, uses device shown in Figure 1, adopts the copper oxide fluid catalyst; Water or alcohol are terminator; With the barkite is raw material, is 160～260 ℃ in temperature of reaction, and reaction pressure is 1.0～8.0MPa; The hydrogen ester mol ratio is 20～200: 1, and reaction velocity is 0.1～5 hour
-1Condition under, raw material contacts with fluid catalyst, reaction generates the elute contain terepthaloyl moietie, wherein, the transformation efficiency of barkite can be reached for 100%, the selectivity of terepthaloyl moietie can obtain better technical effect greater than 95%.
Description of drawings
The fluidized-bed reactor synoptic diagram of Fig. 1 for adopting in the working method of terepthaloyl moietie of the present invention.
A is that emulsion zone, B are that zone of transition, C are negative areas, the 1st among Fig. 1, material inlet, the 2nd, sparger or grid distributor, the 3rd, interchanger, the 4th, riser tube; The 5th, settling vessel, the 6th, divide device soon, the 7th, gas tube, the 8th, cyclonic separator; The 9th, collection chamber, the outlet of 10 product gas, the 11st, stripper, the 12nd, activation inclined tube; The 13rd, inclined tube to be activated, the 14th, stripped vapor inlet, the 15th, terminator inlet.
Raw material is introduced by material inlet 1 among Fig. 1, and through gas distributor or grid distributor 2 laggard emulsion zone A and the catalyzer contact reacts of going into fluidized-bed that distribute, catalyzer and reaction mixture are through zone of transition B entering riser tube 4; Behind vortex quick separation device 6 sharp separation of riser tube 4 upper ends (end); Most of catalyzer gets into the lower region of settling vessel C; The part catalyzer that reaction mixture is carried secretly gets into settling vessel 5 top dilute phase spaces and carries out secondary separation through cyclonic separator 8; Product gas after the separation gets into collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Return the lower region of settling vessel 5 through the dipleg of cyclonic separator 8 from the catalyzer after cyclonic separator 8 separation.The catalyzer to be activated of the C bottom, negative area in the settling vessel 5 gets into stripper 11; Behind stripped vapor stripping from stripped vapor inlet 14; Get into activator (activator omits among the figure) through inclined tube 12 to be activated, the activated inclined tube 12 of acvator gets into fluidized-bed reactor emulsion zone A.In addition, the part catalyzer in the settling vessel 5 continues reaction through the laggard fluidized-bed reactor emulsion zone A of going into of interchanger 3 heat exchange bottom with catalyst mix, and whole process circulation is carried out.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
According to the content preparation catalyzer of the silicon oxide of 20 parts of Cu, 5 parts of Bi and 2 parts of W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten 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.
Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the dimethyl oxalate, is 220 ℃ 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 terepthaloyl moietie, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 94.5%.
[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 Bi and 1 part of W and surplus silicon oxide.Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the dimethyl oxalate, is 250 ℃ in temperature of reaction, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is that the transformation efficiency of dimethyl oxalate is 100% under 35% the condition of 3.0MPa, and the selectivity of terepthaloyl moietie is 96.3%.
[embodiment 3]
By 40 parts of Cu, 3 parts of Bi and 15 parts of W 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, bismuth and the tungsten 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.
Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the oxalic acid diethyl ester, is 200 ℃ in temperature of reaction, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 99%, and the selectivity of terepthaloyl moietie is 93.5%.
[embodiment 4]
By 30 parts of Cu, 1 part of Bi and 8 parts of W 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, bismuth and the tungsten 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.
Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the oxalic acid diethyl ester, is 240 ℃ 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 3.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 99%, and the selectivity of terepthaloyl moietie is 96.7%.
[embodiment 5]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 45 parts of Cu, 8 parts of Bi and 2 parts of W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten 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.
Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the dimethyl oxalate, is 230 ℃ in temperature of reaction, and weight space velocity is 0.3 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.2MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 97.2%.
[embodiment 6]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 25 parts of Cu, 0.8 part of Bi and 4 parts of W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten 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.
Fluidized bed reactor arrangement shown in the accompanying drawing 1 is adopted in test, is raw material with the dimethyl oxalate, is 230 ℃ in temperature of reaction, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is 2.8MPa, and the quality percentage composition of dimethyl oxalate is that the transformation efficiency of dimethyl oxalate is 100% under 14.5% the condition, and the selectivity of terepthaloyl moietie is 98.1%.
[comparative example 1]
Fixed-bed reactor are adopted in test, and according to condition and the catalyzer of embodiment 1, its reaction result is: the transformation efficiency of dimethyl oxalate is 98%, and the selectivity of terepthaloyl moietie is 88%.
Claims (9)
1. the working method of a terepthaloyl moietie is a raw material with the barkite, to be selected from water, C
2～C
5At least a in the alcohol is terminator, may further comprise the steps:
(a) raw material at first gets into from the fluidized-bed reactor bottom, in fluidized-bed reactor emulsion zone and zone of transition and catalyzer contact reacts, forms the elute I that contains terepthaloyl moietie and catalyzer;
(b) the elute I from (a) step contacts with terminator in the bottom, gas-solid sharp separation district on fluidized-bed reactor zone of transition top; Form elute II; Elute II gets into the gas-solid sharp separation district on fluidized-bed reactor top after gas solid separation; Gas gets into follow-up workshop section to be separated, and solid catalyst gets into the activator activation;
(c) return the fluidized-bed reactor bottom dense from the deactivated catalyst of activator and proceed reaction.
2. according to the working method of the said terepthaloyl moietie of claim 1, it is characterized in that emulsion zone in the fluidized-bed reactor links to each other with gas-solid sharp separation district through the zone of transition of undergauge structure.
3. according to the working method of the said terepthaloyl moietie of claim 1, the temperature of reaction that it is characterized in that fluidized-bed reactor is 170～270 ℃, and the barkite weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 40～200: 1, reaction pressure is 1.5～10MPa.
4. according to the working method of the said terepthaloyl moietie of claim 3, it is characterized in that the fluidized-bed reactor temperature of reaction is 180～260 ℃, the barkite weight space velocity is 0.3～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1, reaction pressure is 2.0～6.0MPa.
5. according to the working method of the said terepthaloyl moietie of claim 1; It is characterized in that in the total catalyst 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 bismuth and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 20～300 microns.
6. according to the working method of the said terepthaloyl moietie of claim 5; It is characterized in that in the total catalyst weight umber; Catalyzer comprises that 10～60 parts copper and oxide compound thereof are at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 30～200 microns.
7. according to the working method of the said terepthaloyl moietie of claim 1, it is characterized in that fluidized-bed reactor is selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor.
8. according to the working method of the said terepthaloyl moietie of claim 7, it is characterized in that fluidized-bed reactor is selected from fast fluidized bed.
9. according to the working method of the said terepthaloyl moietie of claim 1, the weight ratio that it is characterized in that raw material and terminator is 5～1000: 1, and the terminator feeding temperature is 10～100 ℃.
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| CN201110047192.8A CN102649705B (en) | 2011-02-25 | 2011-02-25 | Ethylene glycol production method |
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|---|---|---|---|
| CN201110047192.8A CN102649705B (en) | 2011-02-25 | 2011-02-25 | Ethylene glycol production method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848921A (en) * | 2015-07-29 | 2018-03-27 | 巴斯夫欧洲公司 | Method for producing monoethylene glycol |
| CN108383982A (en) * | 2018-01-23 | 2018-08-10 | 浙江省现代纺织工业研究院 | A kind of preparation method of hydridization ethylene glycol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475441A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475441A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848921A (en) * | 2015-07-29 | 2018-03-27 | 巴斯夫欧洲公司 | Method for producing monoethylene glycol |
| CN107848921B (en) * | 2015-07-29 | 2022-01-25 | 巴斯夫欧洲公司 | Process for the production of monoethylene glycol |
| CN108383982A (en) * | 2018-01-23 | 2018-08-10 | 浙江省现代纺织工业研究院 | A kind of preparation method of hydridization ethylene glycol |
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