CN102649076B - Fluidized bed catalyst for catalytic hydrogenation of oxalic ester to obtain ethylene glycol - Google Patents
Fluidized bed catalyst for catalytic hydrogenation of oxalic ester to obtain ethylene glycol Download PDFInfo
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- CN102649076B CN102649076B CN201110045367.1A CN201110045367A CN102649076B CN 102649076 B CN102649076 B CN 102649076B CN 201110045367 A CN201110045367 A CN 201110045367A CN 102649076 B CN102649076 B CN 102649076B
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Abstract
The invention relates to a fluidized bed catalyst for catalytic hydrogenation of oxalic ester to obtain ethylene glycol, which mainly solves the problem that a selectivity of hydrogenation product ethylene glycol is low in the traditional technology. The invention adopts the technical scheme that the fluidized bed catalyst comprises the following components in parts by total weight: 5-80 parts of copper and oxide of copper as active ingredients, at least one of 10-90 parts of silicon oxide, molecular sieve or aluminium oxide as carrier, and 0.01-30 parts of metal element bismuth and tungsten or oxide of metal element bismuth and tungsten as additive; and the average specific surface area of the fluidized bed catalyst carrier is 50-800 square meters per gram, an average particle diameter of the catalyst is 20-300 microns, wherein the weight percentage of the catalyst is taken into account, the catalyst with a particle diameter of 80-150 microns accounts for 20-95 percent of the total weight of the catalyst. According to the invention, the problem is better solved, and the fluidized bed catalyst can be applied in the industrial production of ethylene glycol.
Description
Technical field
The present invention relates to the fluid catalyst that a kind of oxalate catalytic hydrogenation is ethylene glycol, the fluid catalyst that is particularly ethylene glycol about dimethyl oxalate or diethy-aceto oxalate catalysis catalytic hydrogenation.
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, solvent and medium as ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, China has surpassed 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, the powerful development due to 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. UCCSan company substantially.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.As ,UCC company of Shell 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 is compared with catalytic hydration and has significantly been reduced water ratio, 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 than EO direct hydration method, there is larger advantage 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 by traditional petroleum resources, refine for current ethene, and following one period global oil price by the situation of long-term run at high level, with aboundresources, low-cost natural gas or coal, replace Petroleum Production ethylene glycol (Non oil-based route, 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.The carbon monoxide of take is prepared dimethyl oxalate as raw material, by preparation of ethanediol by dimethyl oxalate hydrogenation, is then a very attractive Coal Chemical Industry Route.Both at home and abroad to take the research that carbon monoxide prepares dimethyl oxalate as raw material, obtained good effect now, 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.
The document < < industrial catalyst > > fourth phase in 1996, introduced 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 hydrogenation 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 hydrogenation 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 bismuth of 0.01～30 part and tungsten metallic element or its oxide are auxiliary agent;
Wherein, the average specific surface area of fluid catalyst carrier is 50 meters squared per gram～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 bismuth of 0.05～20 part and tungsten metallic element or its oxide are auxiliary agent.The average specific surface area of carrier is preferably 50 meters squared per gram～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 scope that the catalyst of 80～150 microns accounts for total catalyst weight is 30～90%.Total catalyst weight umber meter, the auxiliary agent umber of bismuth metallic element and its oxide more preferably scope is 0.01～20 part; The auxiliary agent umber of tungsten metallic 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, 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) configure certain density copper, bismuth and tungsten; (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 is 2～6 hours at 300～500 ℃.
Catalyst prepared by the present invention has following characteristics:
1. catalyst adopts spray drying forming, thereby obtain, is suitable for the microspheric catalyst particle that fluid bed uses.
2. in catalyst, the introducing of bismuth and tungsten 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, in reaction temperature, is 160～260 ℃, and 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%, catalyst stability is long, obtains 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]
The content preparation catalyst of pressing the silica of 20wt%Cu+5wt%Bi+2wt%W and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, bismuth and the tungsten 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) with press spray drier, carry out spray shaping, control 100 microns of catalyst granules diameter average out to, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 50%; (e) 120 ℃ dry 6 hours, roasting is 4 hours at 450 ℃.Make fluid catalyst A.
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 the effluent containing ethylene glycol, its reaction result is: the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 92%.
[embodiment 2]
According to each step and the condition of embodiment 1, just shaping of catalyst time control controlling catalyst particle diameter average out to is 150 microns, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 30%, its carrier average specific surface area is 280 meters squared per gram, and the catalyst B making is thus 30wt%Cu+10wt%Bi+1wt%W and surplus silica.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 35% condition that reaction pressure is 3.0MPa, the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 95%.
[embodiment 3]
Press the silica of 40wt%Cu+3wt%Bi+15wt%W and 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, bismuth and the tungsten 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) with press spray drier, carry out spray shaping, control 150 microns of catalyst granules diameter average out to, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 45%; (e) 120 ℃ dry 6 hours, roasting is 4 hours at 450 ℃.Make fluid catalyst C.
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 90%.
[embodiment 4]
Press the silica of 30wt%Cu+1wt%Bi+8wt%W and 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, bismuth and the tungsten 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) with press spray drier, carry out spray shaping, control 120 microns of catalyst granules diameter average out to, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 75%; (e) 120 ℃ dry 6 hours, roasting is 4 hours at 450 ℃.Make fluid catalyst D.
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 91%.
[embodiment 5]
The content preparation catalyst of pressing the ZSM-5 molecular sieve of 45wt%Cu+8wt%Bi+2wt%W and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, bismuth and the tungsten 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) with press spray drier, carry out spray shaping, control 140 microns of catalyst granules diameter average out to, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 40%; (e) 120 ℃ dry 6 hours, roasting is 4 hours at 450 ℃.Make fluid catalyst E.
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 95%.
[embodiment 6]
The content preparation catalyst of pressing the ZSM-5 molecular sieve of 25wt%Cu+0.8wt%Bi+4wt%W and surplus, its step is as follows: (a) mixed nitrate solution and the sodium carbonate liquor of copper, bismuth and the tungsten 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) with press spray drier, carry out spray shaping, control 140 microns of catalyst granules diameter average out to, particle is ball-type, in catalyst weight percentage, particle diameter be the catalyst of 80～150 microns account for total catalyst weight 52%; (e) 120 ℃ dry 6 hours, roasting is 4 hours at 450 ℃.Make fluid catalyst.
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, reaction pressure is 2.8MPa, under the condition that the quality percentage composition of dimethyl oxalate is 14.5%, the conversion ratio of dimethyl oxalate is 100%, ethylene glycol be selectively 98%.
[comparative example 1]
Employing, according to the catalyst of document US4440873, according to each step of embodiment 6 and its reaction result of condition is, the conversion ratio of dimethyl oxalate is 99%, ethylene glycol be selectively 95%.
Claims (5)
1. the fluid catalyst that oxalate catalytic hydrogenation is ethylene glycol, in total catalyst weight umber, by the Cu and its oxides of 5～80 parts, it is active component, in the silica of 10～90 parts, molecular sieve or aluminium oxide, at least one is carrier, and the bismuth of 0.01～30 part and tungsten metallic element or its oxide are that auxiliary agent forms;
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 hydrogenation is ethylene glycol according to claim 1, it is characterized in that in total catalyst weight umber, by the Cu and its oxides of 10～60 parts, it is active component, in the silica of 15～90 parts or aluminium oxide, at least one is carrier, and the bismuth of 0.05～20 part and tungsten metallic element or its oxide are that auxiliary agent forms.
3. the fluid catalyst that oxalate catalytic hydrogenation 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 30～90%.
4. the fluid catalyst that oxalate catalytic hydrogenation is ethylene glycol according to claim 2, is characterized in that in total catalyst weight umber, and the auxiliary agent umber of bismuth metallic element and its oxide is 0.01～20 part; The auxiliary agent umber of tungsten metallic element and its oxide is 0.01～20 part.
5. the fluid catalyst that oxalate catalytic hydrogenation is ethylene glycol according to claim 1, take fluid bed as reactor, take polybasic ester 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 reaction velocity is 0.1～5 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 CN201110045367.1A patent/CN102649076B/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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