CN102649071A - Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol - Google Patents
Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol Download PDFInfo
- Publication number
- CN102649071A CN102649071A CN2011100453525A CN201110045352A CN102649071A CN 102649071 A CN102649071 A CN 102649071A CN 2011100453525 A CN2011100453525 A CN 2011100453525A CN 201110045352 A CN201110045352 A CN 201110045352A CN 102649071 A CN102649071 A CN 102649071A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ethylene glycol
- oxide
- oxalate
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol, and mainly solves the problem of low selectivity of hydrogenation product ethylene glycol in the prior art. In terms of total parts by weight of the catalyst, the fluidized bed catalyst comprises the following components: 5-80 parts of copper and oxide thereof serving as an active ingredient, 10-90 parts of at least one of silicon oxide, molecular sieve or aluminum oxide serving as a carrier and 0.01-30 parts of cerium and niobium metal elements or oxides thereof serving as an auxiliary agent, wherein the average specific surface area of the carrier of the fluidized bed catalyst is 50-800 square meters per gram; and the average particle diameter of the catalyst is 20-300 microns. According to the technical scheme, the problem is solved well; and the fluidized bed catalyst can be used in the industrial production of catalytic reaction of oxalate into ethylene glycol.
Description
Technical field
The fluid catalyst that to the present invention relates to a kind of oxalate catalytic reaction be ethylene glycol is the fluid catalyst of ethylene glycol about dimethyl oxalate or diethy-aceto oxalate catalytic reaction particularly.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals; Be mainly used in to produce and gather vinegar fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent 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 ethylene glycol consumption of the first in the world big country, and domestic apparent consumption figure average annual growth rate reached 17.4% in 2001～2006 years.Though China's ethylene glycol production capacity 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 demand.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts the oxirane direct hydration, i.e. the legal process route of pressure (hydraulic) 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 ethylene glycol is also making progress always.Developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession like Shell company, UCC company, Moscow Mendeleev 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 ethylene carbonate legal system ethylene glycol production technology in succession; Companies such as Dow chemistry have developed EG and dimethyl carbonate (DMC) coproduction preparing ethylene glycol production technology etc.
For product water content height, follow-up equipment (evaporimeter) 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 conversion ratio and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalysis hydration system EG replacement on-catalytic hydrating process is trend of the times so.No matter the technology that ethylene carbonate (EC) legal system is equipped with EG aspect EO conversion ratio, EG selectivity, still all has bigger advantage than EO direct hydration method aspect raw material, the energy consumption, is a kind of method that maintains the leading position.EG and DMC co-production technology can make full use of the CO of ethene oxidation by-product
2Resource in existing EO process units, 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 said 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 Petroleum Production ethylene glycol (non-petroleum path is the CO route again) with aboundresources, low-cost natural gas or coal, can possess the advantage of competing mutually with traditional ethene route.Wherein, synthesis gas synthesizes the EG new technology, may produce great influence to the innovation of EG production technology.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, commercial 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 ethylene glycol and also need more carry out work in a deep going way how.
Document " industrial catalyst " fourth phase in 1996, introduced diethy-aceto oxalate hydrogenation preparing ethylene glycol mould examination research for 24～29 pages, its catalyst that adopts is in the oxalate course of reaction, and glycol selectivity is lower than 90%.
Document " Chemical Reaction Engineering and technology " was rolled up the 121st～128 page of the 2nd phase in 2004 the 20th and has been introduced a kind of employing Cu/SiO
2The research of dimethyl oxalate hydrogenation reaction on the catalyst, but the glycol selectivity of this catalyst is lower than 90%.
The problem that above-mentioned technical literature exists is problems such as the selectivity of ethylene glycol is low.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of hydrogenation products glycol selectivity that in the past exists in the technology.It is the fluid catalyst of ethylene glycol that a kind of new oxalate catalytic reaction is provided.This catalyst has the high advantage of hydrogenation products 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 oxalate catalytic reaction is the fluid catalyst of ethylene glycol; In the total catalyst weight umber; Copper and the oxide thereof that comprises 5～80 parts is at least aly in active component, 10～90 parts silica, molecular sieve or the aluminium oxide to be carrier, and 0.01～30 part cerium and niobium metal element or its oxide are auxiliary agent;
Wherein, The average specific surface area of fluid catalyst carrier is 50～800 meters squared per gram; The average particulate diameter of catalyst is 20～300 microns, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 20～95%.
In the technique scheme in the total catalyst weight umber; Copper and the oxide thereof that comprises 10～60 parts is at least aly in active component, 15～90 parts silica or the aluminium oxide to be carrier, and 0.05～20 part cerium and niobium metal element or its oxide are auxiliary agent.The average specific surface area of carrier is preferably 50～600 meters squared per gram; The average particulate diameter of catalyst is preferably 50～200 microns, and in catalyst weight percentage, particle diameter is that the preferred proportion that 80～150 microns catalyst accounts for total catalyst weight is 30～95%.Total catalyst weight umber meter, the auxiliary agent umber of ce metal element and its oxide more preferably scope is 0.01～20 part; The auxiliary agent umber of niobium metal element and its oxide more preferably scope is 0.01～20 part.
Catalyst in the technique scheme is a reactor with the fluid bed, is raw material with the polybasic ester, and range of reaction temperature is 160～260 ℃, and reaction pressure is 1.0～8.0MPa, and hydrogen/ester mol ratio is 20～200: 1, and reaction velocity is 0.1～5 hour
-1
The concrete preparation process of new catalyst provided by the invention is: the mixed nitrate solution and the sodium carbonate liquor that (a) dispose 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 cyclic washing, until no Na
+The back adds the binding agent making beating; (d) with the press spray drier by the requirement granularity carry out spray shaping, 20～300 microns of catalyst granules diameter average out to are preferably 50～200 microns, particle is ball-type; (e) 120 ℃ of dryings are 4～10 hours, 300～500 ℃ of following roastings 2～6 hours.
The catalyst of the present invention's preparation has following characteristics:
1. catalyst adopts spray drying forming, thereby obtains to be suitable for the microspheric catalyst particle that fluid bed uses.
2. the introducing of cerium and niobium auxiliary agent makes catalyst show catalytic performance preferably in the catalyst.
Adopting the fluid catalyst of the present invention and the present invention preparation, adopt fluidized-bed reactor, is being raw material with the oxalate; In reaction temperature is 160～260 ℃; Reaction pressure is 1.0～8.0MPa, and hydrogen // ester mol ratio is 20～200: 1, and weight space velocity is 0.2～5 hour
-1Condition under the conversion ratio of oxalate can reach 100%, the selectivity of ethylene glycol can obtain better technical effect greater than 95%.
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]
In parts by weight, according to 20 parts Cu, 5 parts the content preparation catalyst of silica of Nd and surplus of Ce and 2 parts, its step is following: (a) mixed nitrate solution and the sodium carbonate liquor 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 cyclic washing, until no Na
+Back adding silica support (specific area 150 meters squared per gram) and concentration are 10% silica sol binder making beating; (d) carry out spray shaping with the press spray drier, 100 microns of control catalyst granules 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, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 20%.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 220 ℃ in reaction temperature, 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 effluent that contains ethylene glycol, and its reaction result is: the conversion ratio of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96%.
[embodiment 2]
Each step and condition according to embodiment 1; Just shaping of catalyst time control controlling catalyst particle diameter average out to is 150 microns; Particle is ball-type, and its carrier average specific surface area is 280 meters squared per gram, in catalyst weight percentage; Particle diameter be 80～150 microns catalyst account for total catalyst weight 35%, the catalyst B that makes is thus counted 30 parts of Cu, 10 parts of Ce and 1 part of Nd and surplus silica with parts by weight.Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 250 ℃ in reaction temperature, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 3.0MPa, and the conversion ratio of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96%.
[embodiment 3]
By 40 parts of Cu, 3 parts of Ce and 15 parts of Nd and the silica of surplus and the content preparation catalyst of aluminium oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate liquor 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 cyclic washing, until no Na
+Back adding alumina support (specific area 300 meters squared per gram) and concentration are 15% silica sol binder making beating; (d) carry out spray shaping with the press spray drier, 150 microns of control catalyst granules 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, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 40%.
Adopting fluidized-bed reactor, is raw material with the diethy-aceto oxalate, is 200 ℃ in reaction temperature, 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 conversion ratio of diethy-aceto oxalate is 99%, and the selectivity of ethylene glycol is 94%.
[embodiment 4]
By 30 parts of Cu, 1 part of Ce and 8 parts of Nd and the silica of surplus and the content preparation catalyst of aluminium oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate liquor 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 cyclic washing, until no Na
+Back adding alumina support (specific area 100 meters squared per gram) and concentration are 6% silica sol binder making beating; (d) carry out spray shaping with the press spray drier, 120 microns of control catalyst granules 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, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 75%.
Adopting fluidized-bed reactor, is raw material with the diethy-aceto oxalate, is 240 ℃ 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 3.8MPa, and the conversion ratio of diethy-aceto oxalate is 99%, and the selectivity of ethylene glycol is 94%.
[embodiment 5]
By the content preparation catalyst of the ZSM-5 molecular sieve of 45 parts of Cu, 8 parts of Ce and 2 parts of Nd and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate liquor 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 cyclic washing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific area 450 meters squared per gram) making beating; (d) carry out spray shaping with the press spray drier, 140 microns of control catalyst granules 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, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 30%.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 230 ℃ in reaction temperature, 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 conversion ratio of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96%.
[embodiment 6]
By the content preparation catalyst of the ZSM-5 molecular sieve of 25 parts of Cu, 0.8 part of Ce and 4 parts of Nd and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate liquor 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 cyclic washing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific area 400 meters squared per gram) making beating; (d) carry out spray shaping with the press spray drier, 140 microns of control catalyst granules 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 F, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 50%.
Adopting fluidized-bed reactor, is raw material with the dimethyl oxalate, is 230 ℃ in reaction temperature, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.8MPa, and the conversion ratio of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98%.
[comparative example 1]
Adopt document " industrial catalyst " fourth phase in 1996; The catalyst of the diethy-aceto oxalate hydrogenation preparing ethylene glycol of 24～29 pages of introductions; Each step and its reaction result of condition according to embodiment 6 do, the conversion ratio of dimethyl oxalate is 99%, and the selectivity of ethylene glycol is 89%.
Claims (5)
1. fluid catalyst that the oxalate catalytic reaction is an ethylene glycol; In the total catalyst weight umber; Copper and the oxide thereof that comprises 5～80 parts is at least aly in active component, 10～90 parts silica, molecular sieve or the aluminium oxide to be carrier, and 0.01～30 part cerium and niobium metal element or its oxide are auxiliary agent;
Wherein, The average specific surface area of fluid catalyst carrier is 50～800 meters squared per gram; The average particulate diameter of catalyst is 20～300 microns, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 20～95%.
2. the fluid catalyst that is ethylene glycol according to the said oxalate catalytic reaction of claim 1; It is characterized in that in the total catalyst weight umber; Copper and the oxide thereof that comprises 10～60 parts is at least aly in active component, 15～90 parts silica or the aluminium oxide to be carrier, and 0.05～20 part cerium and niobium metal element or its oxide are auxiliary agent.
3. the fluid catalyst that is ethylene glycol according to the said oxalate catalytic reaction of claim 1, the average specific surface area that it is characterized in that carrier is 50～600 meters squared per gram; The average particulate diameter of catalyst is 50～200 microns, in catalyst weight percentage, particle diameter be 80～150 microns catalyst account for total catalyst weight 30～95%.
4. the fluid catalyst that is ethylene glycol according to the said oxalate catalytic reaction of claim 2 is characterized in that in the total catalyst weight umber, and the auxiliary agent umber of ce metal element and its oxide is 0.01～20 part; The auxiliary agent umber of niobium metal element and its oxide is 0.01～20 part.
5. the fluid catalyst that is ethylene glycol according to the said oxalate catalytic reaction of claim 1; With the fluid bed is reactor; With the polybasic ester is raw material, and range of reaction temperature is 160～260 ℃, and reaction pressure is 1.0～8.0MPa; Hydrogen/ester mol ratio is 20～200: 1, and reaction velocity is 0.1～5 hour
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045352.5A CN102649071B (en) | 2011-02-25 | 2011-02-25 | Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045352.5A CN102649071B (en) | 2011-02-25 | 2011-02-25 | Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102649071A true CN102649071A (en) | 2012-08-29 |
| CN102649071B CN102649071B (en) | 2014-05-28 |
Family
ID=46691292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110045352.5A Active CN102649071B (en) | 2011-02-25 | 2011-02-25 | Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649071B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628129A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol |
| CN101138725A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101879448A (en) * | 2010-06-24 | 2010-11-10 | 天津大学 | Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof |
-
2011
- 2011-02-25 CN CN201110045352.5A patent/CN102649071B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628129A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol |
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101138725A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same |
| CN101879448A (en) * | 2010-06-24 | 2010-11-10 | 天津大学 | Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649071B (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101138725B (en) | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same | |
| CN101992115B (en) | High selective catalyst | |
| CN101992127A (en) | Catalyst reduction method | |
| CN102649073A (en) | Preparation method of fluid catalyst for production of ethanediol by oxalate through hydrogenation | |
| CN102649081B (en) | Reducing method for preparation of ethylene glycol catalyst by oxalate through hydrogenation | |
| US9102583B2 (en) | Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction | |
| CN102649698B (en) | The efficient production method of ethylene glycol | |
| CN102649686A (en) | Method for synthesizing ethylene glycol | |
| CN102649706A (en) | Method for preparing ethylene glycol through gas phase hydrogenation of oxalate | |
| CN102649094A (en) | Method for reducing catalyst used in hydrogenation production of ethylene glycol from oxalate | |
| CN102649076B (en) | Fluidized bed catalyst for catalytic hydrogenation of oxalic ester to obtain ethylene glycol | |
| CN102649695B (en) | High-efficiency production method for ethylene glycol | |
| CN102649071B (en) | Fluidized bed catalyst used in catalytic reaction of oxalate into ethylene glycol | |
| CN102649693B (en) | Method for preparing ethylene glycol through catalytic hydrogenation by oxalic ester | |
| CN102649705B (en) | Ethylene glycol production method | |
| CN102649078B (en) | Catalyst for production of ethylene glycol by oxalate through hydrogenation | |
| CN102649064B (en) | Method for generating ethylene glycol through fluidized-bed reaction of oxalate | |
| CN102649703B (en) | Method adopting oxalate to produce ethylene glycol | |
| CN102649075B (en) | Method for producing ethylene glycol by oxalate through fluidized bed catalytic reaction | |
| CN102649694B (en) | Oxalate through hydrogenation is the method for ethylene glycol | |
| CN101993346A (en) | Method for hydrogenating oxalic ester into glycol | |
| CN102649707A (en) | Method for preparing ethylene glycol by gas-phase hydrogenating oxalate | |
| CN102649685A (en) | Method for producing ethylene glycol efficiently by oxalic ester | |
| CN102649700B (en) | Method for synthesizing ethylene glycol | |
| CN102649708B (en) | Method for producing ethylene glycol through high-efficiency catalytic reaction of oxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |