CN102649071B - 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
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- CN102649071B CN102649071B CN201110045352.5A CN201110045352A CN102649071B CN 102649071 B CN102649071 B CN 102649071B CN 201110045352 A CN201110045352 A CN 201110045352A CN 102649071 B CN102649071 B CN 102649071B
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- 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
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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 present invention relates to the fluid catalyst that a kind of oxalate catalytic reaction is ethylene glycol, the fluid catalyst that is particularly ethylene glycol about dimethyl oxalate or diethy-aceto oxalate catalytic reaction.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of poly-vinegar fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent and explosive etc., can be used in addition the industries such as coating, soup, brake-fluid and ink, as solvent and the medium of ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, China has exceeded the U.S. becomes the large ethylene glycol consumption of the first in the world big country, and within 2001～2006 years, domestic apparent consumption amount average annual growth rate reaches 17.4%.Although China's ethylene glycol capacity and output increases very fast, due to the powerful development of the industry such as polyester, still can not meet the growing market demand, all need every year a large amount of imports, and import volume is increase year after year situation.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts 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 tri-companies substantially.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.As Shell company, UCC company, Moscow Mendeleev chemical engineering institute, oil of SPC institute etc. have developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession; The 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; The companies such as Dow chemistry have developed EG and dimethyl carbonate (DMC) coproduction preparing ethylene glycol production technology etc.
Product water content for direct hydration method is high, follow-up equipment (evaporimeter) long flow path, equipment is large, energy consumption is high, process total recovery only has 70% left and right, directly affects the production cost of EG.Direct hydration method has significantly reduced water ratio compared with catalytic hydration, has obtained higher EO conversion ratio and EG selective simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalysis hydration EG replacement processed on-catalytic hydrating process is trend of the times so.Ethylene carbonate (EC) legal system for the technology of EG no matter EO conversion ratio, EG selective aspect, or all there is larger advantage than EO direct hydration method aspect raw material, energy consumption, be a kind of method maintaining the leading position.EG and DMC co-production technology can make full use of the CO of ethylene by-product
2resource, in existing EO process units, only needs the reactions steps that increases production EC just can produce two kinds of very value products, very attractive.
But the common shortcoming of said method is to need consumption of ethylene resource, and mainly refine by traditional petroleum resources for current ethene, and following one period global oil price by the situation of long-term run at high level, replace Petroleum Production ethylene glycol (Non oil-based route with aboundresources, low-cost natural gas or coal, be again CO route), can possess the advantage of competing mutually with traditional ethene route.Wherein, synthesis gas synthesizes EG new technology, may produce great impact to the innovation of EG production technology.Preparing dimethyl oxalate take carbon monoxide as raw material, is then a very attractive Coal Chemical Industry Route by preparation of ethanediol by dimethyl oxalate hydrogenation.Now the research of preparing dimethyl oxalate take carbon monoxide as raw material has been obtained to good effect both at home and abroad, industrial production is ripe.And by preparation of ethanediol by dimethyl oxalate hydrogenation, still have the further investigation of more need of work, especially how effectively improve in ethylene glycol selective and also need more to carry out in a deep going way work.
Document " industrial catalyst " fourth phase in 1996, introduce diethy-aceto oxalate Hydrogenation ethylene glycol mould examination research for 24～29 pages, its catalyst adopting is in oxalate course of reaction, and glycol selectivity is lower than 90%.
121st～128 pages of document " Chemical Reaction Engineering and technique " the 20th the 2nd phases of volume in 2004 have been introduced a kind of employing Cu/SiO
2the research of Hydrogenation of Dimethyl Oxalate reaction on catalyst, but the glycol selectivity of this catalyst is lower than 90%.
The problem that above-mentioned technical literature exists is the problem such as selective low of ethylene glycol.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of hydrogenation products glycol selectivity existing in conventional art.The fluid catalyst that a kind of new oxalate catalytic reaction is ethylene glycol is provided.This catalyst has advantages of that hydrogenation products glycol selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the fluid catalyst that a kind of oxalate catalytic reaction is ethylene glycol, in total catalyst weight umber, the Cu and its oxides that comprises 5～80 parts is that in active component, silica, molecular sieve or the aluminium oxide of 10～90 parts, at least one is carrier, and the cerium of 0.01～30 part 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 the catalyst of 80～150 microns account for total catalyst weight 20～95%.
In technique scheme in total catalyst weight umber, the Cu and its oxides that comprises 10～60 parts is that in active component, the silica of 15～90 parts or aluminium oxide, at least one is carrier, and the cerium of 0.05～20 part 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 the catalyst of 80～150 microns 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 technique scheme, take fluid bed as reactor, take polybasic ester as raw material, 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) configure certain density copper, cerium and niobium; (b) above-mentioned solution co-precipitation at 60～80 ℃, constantly stirs in precipitation process, pH=5～8 when precipitation stops; (C) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add binding agent making beating; (d) with press spray drier by 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 ℃ dry 4～10 hours, roasting 2～6 hours at 300～500 ℃.
Catalyst prepared by the present invention has following characteristics:
1. catalyst adopts spray drying forming, is suitable for thereby obtain the microspheric catalyst particle that fluid bed uses.
2. the introducing of Cerium in Catalysts and niobium auxiliary agent makes catalyst show good catalytic performance.
The fluid catalyst that adopts the present invention and the present invention to prepare, adopts fluidized-bed reactor, take oxalate as raw material, it is 160～260 ℃ in reaction temperature, 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%, ethylene glycol selectively can be greater than 95%, obtain good technique effect.
Below by embodiment and comparative example, the invention will be further elaborated, but be not limited only to the present embodiment.
the specific embodiment
[embodiment 1]
In parts by weight, according to the content preparation catalyst of the silica of the Nb of the Cu of 20 parts, the Ce of 5 parts and 2 parts and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution co-precipitation at 70 ℃, constantly stirs in precipitation process, PH=6 when precipitation stops; (c) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add the making beating of silica sol binder that silica support (specific area 150 meters squared per gram) and concentration are 10%; (d) carry out spray shaping with press spray drier, control 100 microns of catalyst granules diameter average out to, particle is ball-type; (e) 120 ℃ dry 6 hours, roasting 4 hours at 450 ℃.Make fluid catalyst A, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 20%.
Adopting fluidized-bed reactor, take dimethyl oxalate as raw material, is 220 ℃ in reaction temperature, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, under the condition that reaction pressure is 2.8MPa, raw material contacts with catalyst A, reaction generates containing the effluent of ethylene glycol, its reaction result is: the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 96%.
[embodiment 2]
According to each step and the condition of embodiment 1, just 150 microns of shaping of catalyst time control controlling catalyst particle diameter average out to, particle is ball-type, its carrier average specific surface area is 280 meters squared per gram, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 35%, the catalyst B making is thus counted 30 parts of Cu, 10 parts of Ce and 1 part of Nb and surplus silica with parts by weight.Adopting fluidized-bed reactor, take dimethyl oxalate as raw material, is 250 ℃ in reaction temperature, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, under the condition that reaction pressure is 3.0MPa, the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 96%.
[embodiment 3]
By 40 parts of Cu, 3 parts of Ce and 15 parts of Nb and the silica of surplus and the content of aluminium oxide preparation catalyst, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution co-precipitation at 65 ℃, constantly stirs in precipitation process, pH=7 when precipitation stops; (c) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add the making beating of silica sol binder that alumina support (specific area 300 meters squared per gram) and concentration are 15%; (d) carry out spray shaping with press spray drier, control 150 microns of catalyst granules diameter average out to, particle is ball-type; (e) 120 ℃ dry 6 hours, roasting 4 hours at 450 ℃.Make fluid catalyst C, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 40%.
Adopting fluidized-bed reactor, take diethy-aceto oxalate as raw material, is 200 ℃ in reaction temperature, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, under the condition that reaction pressure is 2.8MPa, the conversion ratio of diethy-aceto oxalate is 99%, ethylene glycol be selectively 94%.
[embodiment 4]
By 30 parts of Cu, 1 part of Ce and 8 parts of Nb and the silica of surplus and the content of aluminium oxide preparation catalyst, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution co-precipitation at 65 ℃, constantly stirs in precipitation process, pH=7 when precipitation stops; (c) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add the making beating of silica sol binder that alumina support (specific area 100 meters squared per gram) and concentration are 6%; (d) carry out spray shaping with press spray drier, control 120 microns of catalyst granules diameter average out to, particle is ball-type; (e) 120 ℃ dry 6 hours, roasting 4 hours at 450 ℃.Make fluid catalyst D, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 75%.
Adopting fluidized-bed reactor, take diethy-aceto oxalate as raw material, is 240 ℃ in reaction temperature, and weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 60: 1, under the condition that reaction pressure is 3.8MPa, the conversion ratio of diethy-aceto oxalate is 99%, ethylene glycol be selectively 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 Nb and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution co-precipitation at 65 ℃, constantly stirs in precipitation process, pH=5 when precipitation stops; (c) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add ZSM-5 molecular sieve carrier (specific area 450 meters squared per gram) making beating; (d) carry out spray shaping with press spray drier, control 140 microns of catalyst granules diameter average out to, particle is ball-type; (e) 120 ℃ dry 6 hours, roasting 4 hours at 450 ℃.Make fluid catalyst E, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 30%.
Adopting fluidized-bed reactor, take dimethyl oxalate as raw material, is 230 ℃ in reaction temperature, and weight space velocity is 0.3 hour
-1, hydrogen/ester mol ratio is 70: 1, under the condition that reaction pressure is 2.2MPa, the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 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 Nb and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, cerium and the niobium of configuration desired concn; (b) above-mentioned solution co-precipitation at 65 ℃, constantly stirs in precipitation process, pH=5 when precipitation stops; (c) by above-mentioned sediment slurry deionized water cyclic washing, until without Na
+after add ZSM-5 molecular sieve carrier (specific area 400 meters squared per gram) making beating; (d) carry out spray shaping with press spray drier, control 140 microns of catalyst granules diameter average out to, particle is ball-type; (e) 120 ℃ dry 6 hours, roasting 4 hours at 450 ℃.Make fluid catalyst F, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 50%.
Adopting fluidized-bed reactor, take dimethyl oxalate as raw material, is 230 ℃ in reaction temperature, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, under the condition that reaction pressure is 2.8MPa, the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 98%.
[comparative example 1]
Adopt document " industrial catalyst " fourth phase in 1996, the catalyst of the diethy-aceto oxalate Hydrogenation ethylene glycol of 24～29 pages of introductions, according to each step of embodiment 6 and its reaction result of condition be, the conversion ratio of dimethyl oxalate is 99%, ethylene glycol be selectively 89%.
Claims (5)
1. the fluid catalyst that oxalate catalytic reaction is ethylene glycol, in total catalyst weight umber, be active component by the Cu and its oxides of 5～80 parts, in silica, molecular sieve or the aluminium oxide of 10～90 parts, at least one is carrier, and the cerium of 0.01～30 part and niobium metal element or its oxide are auxiliary agent composition;
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 the catalyst of 80～150 microns account for total catalyst weight 20～95%.
2. the fluid catalyst that oxalate catalytic reaction is ethylene glycol according to claim 1, it is characterized in that in total catalyst weight umber, be active component by the Cu and its oxides of 10～60 parts, in the silica of 15～90 parts or aluminium oxide, at least one is carrier, and the cerium of 0.05～20 part and niobium metal element or its oxide are auxiliary agent composition.
3. the fluid catalyst that oxalate catalytic reaction is ethylene glycol according to 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 the catalyst of 80～150 microns account for total catalyst weight 30～95%.
4. the fluid catalyst that oxalate catalytic reaction is ethylene glycol according to claim 2, is characterized in that in 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 oxalate catalytic reaction is ethylene glycol according to claim 1, take fluid bed as reactor, take oxalate as raw material, range of reaction temperature is 160～260 ℃, reaction pressure is 1.0～8.0MPa, hydrogen/ester mol ratio is 20～200: 1, and weight space velocity is 0.2～5 hour
-1.
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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 | Catalyst for synthesizing ethylene glycol by hydrogenation of oxalate and preparation method thereof |
| 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 | Regular structure catalyst for hydrogenation of oxalate to ethylene glycol and preparation method thereof |
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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 | Catalyst for synthesizing ethylene glycol by hydrogenation of oxalate and preparation method thereof |
| CN101879448A (en) * | 2010-06-24 | 2010-11-10 | 天津大学 | Regular structure catalyst for hydrogenation of oxalate to ethylene glycol and preparation method thereof |
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