CN102649695B - High-efficiency production method for ethylene glycol - Google Patents
High-efficiency production method for ethylene glycol Download PDFInfo
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Abstract
The invention relates to a high-efficiency production method for ethylene glycol, and mainly solves the technical problem low selectivity of ethylene glycol in the prior art. Through the adoption of the technical scheme that oxalic ester is taken as a raw material, copper contained oxide or other oxide is taken as a catalyst, and under the conditions that the reaction temperature is 170 to 270 DEG C, the weight space velocity of oxalic ester is 0.2 to 5 hours<-1>, the mol ratio of hydrogen to ester is (40 to 200) : 1, and the reaction pressure is 1.5 to 10 MPa, the raw material is in contact with the catalyst in a reactor to generate an ethylene glycol contained effluent, wherein the reactor is a sub-zone heat exchanging pipe reactor adopting an inner pipe and outer pipe sleeved structure to carry out heat exchange on the catalyst, and the invention solves the problem of low selectivity of ethylene glycol well, and can be used in the industrial production of ethylene glycol.
Description
Technical field
The present invention relates to a kind of method of high efficiency production ethylene glycol, particularly about adopting subregion heat exchanging pipe reactor and adopting the sleeve structure heat exchange of inner and outer tubes to realize the method for dimethyl oxalate or oxalic acid diethyl ester hydrogenation generating glycol.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of poly-vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for the industries such as coating, soup, brake fluid and ink in addition, 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 first in the world large ethylene glycol consumption big country, and within 2001 ~ 2006 years, domestic Apparent con-sumption average annual growth rate reaches 17.4%.Although China 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 requirement, all need a large amount of import every year, and import volume is in growing trend year by year.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts oxyethane direct hydration, the operational path that namely pressurized water is legal, and production technology monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC tri-company 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 Mendelyeev chemical engineering institute, oil of SPC institute etc. develop 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 develop NSC 11801 legal system ethylene glycol production technology; The companies such as Dow chemistry develop EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
Reaction product water content for direct hydration method is high, follow-up equipment (vaporizer) long flow path, equipment is large, energy consumption is high, process total recovery only has about 70%, directly affects the production cost of EG.Direct hydration method considerably reduces water ratio compared with catalytic hydration, obtains higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, so EO catalytic hydration EG replace on-catalytic hydrating process to be trend of the times.NSC 11801 (EC) legal system no matter in EO transformation efficiency, EG selectivity, or all has larger advantage than EO direct hydration method for the technology of EG in raw material, energy expenditure, is a kind of method maintained 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 need increase the reactions steps of producing EC and just can produce two kinds of very value products, very attractive.
But the common drawback of aforesaid method needs consumption of ethylene resource, and for current ethene mainly by the refining of traditional petroleum resources, and when future, one period, global oil price was by long-term run at high level, oil production ethylene glycol (Non oil-based route is replaced with aboundresources, low-cost Sweet natural gas or coal, be again CO route), the advantage of competing mutually with traditional ethene route can be possessed.Wherein, synthetic gas synthesis EG new technology, may produce great impact to the innovation of EG production technique.Being that dimethyl oxalate prepared by raw material with carbon monoxide, is then a very attractive Coal Chemical Industry Route by preparation of ethanediol by dimethyl oxalate hydrogenation.Now domestic and international to being that the research that dimethyl oxalate prepared by raw material achieves good effect with carbon monoxide, industrial production is ripe.And by preparation of ethanediol by dimethyl oxalate hydrogenation, still have more need of work to further investigate, especially also well do not break through in the selectivity how effectively improving ethylene glycol and raising catalyst stability.
Document " spectrographic laboratory " 27 volume 2 phase 616-619 pages in 2010 disclose the research of one section of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen, and it has prepared Cu-B/ γ-Al by chemical reduction-deposition
2o
3, Cu-B/SiO
2amorphous alloy catalyst, its evaluation result shows, 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 technique thereof is lower, and generally about 96%, the selectivity of ethylene glycol is about about 92%.
The subject matter that above-mentioned document exists is that glycol selectivity is lower, needs to improve further and improve.
Summary of the invention
Technical problem to be solved by this invention is the problem that the glycol selectivity that exists in conventional art is low.A kind of method of new high efficiency production ethylene glycol is provided.The method has the high advantage of glycol selectivity.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of high efficiency production ethylene glycol, take barkite as raw material, with cupric or its oxide compound for catalyzer, be 170 ~ 270 DEG C in temperature of reaction, barkite weight space velocity is 0.2 ~ 5 hour
-1hydrogen/ester mol ratio is 40 ~ 200: 1, reaction pressure is under 1.5 ~ 10MPa condition, raw material contacts with catalyst reactor, generate the effluent containing ethylene glycol, it is characterized in that, described reactor is subregion heat exchange and adopts the sleeve structure of inner and outer tubes catalyzer to be carried out to the shell-and-tube reactor of heat exchange.
In technique scheme, the reaction conditions of reactor is preferably: temperature of reaction is 180 ~ 260 DEG C, and barkite weight space velocity is 0.3 ~ 3 hour
-1, hydrogen/ester mol ratio is 50 ~ 150: 1, and reaction pressure is 2.0 ~ 6.0MPa.Catalyzer preferred version is in total catalyst weight number, the Cu and its oxides that catalyzer comprises 5 ~ 80 parts be active ingredient, 10 ~ 90 parts silicon oxide, at least one is carrier in molecular sieve or aluminum oxide, and the bismuth of 0.01 ~ 30 part and tungsten metallic element or its oxide compound are auxiliary agent.Catalyzer more preferably scheme in total catalyst weight number, the Cu and its oxides that catalyzer comprises 10 ~ 60 parts is active ingredient, at least one is carrier in the silicon oxide of 15 ~ 90 parts or aluminum oxide, and the bismuth of 0.05 ~ 20 part and tungsten metallic element or its oxide compound are auxiliary agent.
In technique scheme, the reactor of inventive method is primarily of feed(raw material)inlet (1), feed(raw material)inlet (2), gas distributing chamber (26), gas distributing chamber (27), gas quadratic distribution room (24), bundle of reaction tubes outer tube (5), pipe (28) in bundle of reaction tubes, catalyst bed (7), collection chamber (13), porous gas collection plate (11), form with product exit (12), it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22) according to reaction gas flow direction order, second heat exchange block (19) and the 3rd heat exchange block (16), first heat exchange block (22) and first district's heat transferring medium export (23) and are connected with first district's heat transferring medium entrance (21), second heat exchange block (19) exports (20) with second district's heat transferring medium entrance (8) with second district's heat transferring medium and is connected, and exports (17) be connected with the 3rd heat exchange block (16) with the 3rd district's heat transferring medium entrance (15) with the 3rd district's heat transferring medium.
Arrange pipe (28) in bundle of reaction tubes in technique scheme in catalyst bed (7), in bundle of reaction tubes, pipe (28) is connected with gas distributing chamber (26) and the gas distributing chamber (27) in collection chamber (13) by inlet gas connecting hose (29).Porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product exit (12).Separated by the first subregion dividing plate (6) between first heat exchange block (22) and the second heat exchange block (19), separated by the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).Be 1/8 ~ 1/3 of reactor length under first subregion dividing plate (6) distance reactor cover plate (25); Be 1/8 ~ 1/3 of reactor length under second subregion dividing plate (9) distance the first subregion dividing plate (6).
Due to catalyzed reaction on a catalyst and carry out not according to front and back equal velocity, General reactions device is anterior from balanced remote, speed of response is fast, release reaction heat also many, rear portion is with the close balance of reaction, speed of response slows down, release reaction heat also few, if the same before and after the temperature of refrigerant, if reduce coolant temperature like this, strengthen heat transfer temperature difference and move heat, what reach top or anterior high speed of response and strong reaction heat moves heat request, then reactor lower part or rear portion reaction heat reduce, move heat to be greater than reaction heat and to cause temperature of reaction to decline, speed of response is made to slow down until with regard to stopped reaction below catalyst activity further, therefore be difficult to accomplish that the way made the best of both worlds of all carrying out under optimal reaction temperature is reacted in front and rear part.The present invention is directed to this fundamental contradiction, break through the refrigerant of existing same temperature, and adopt the different section of reactor to adopt differing temps refrigerant to solve, heat exchange in reaction is made to need design by the size that reaction heat shifts out, multiple pieces of districts before and after specifically can being divided into by reaction gas flow direction order in catalyst layer, carry out indirect heat exchange by refrigerant by heat transfer tube.On the other hand, the present invention is for the reaction heat of catalyzer, also adopt in catalyst bed and interior pipe is set, and counter-current flow unstripped gas, carrying out preheating to unstripped gas has saved energy consumption on the one hand, optimize reaction bed temperature distribution simultaneously, thus realizing the equiblibrium mass distribution of full bed temperature, this, for the efficiency of maximized performance catalyzer, farthest reduces the loss of barkite, improve the selectivity of ethylene glycol, useful effect is provided.
The high-efficiency method for producing of ethylene glycol of the present invention, adopt Fig. 1 shown device, adopt subregion heat exchange, precise control of temperature, adopts the sleeve structure of inner and outer tubes to carry out heat exchange to catalyzer simultaneously, adopt copper oxide catalyzer, taking barkite as raw material, is 160 ~ 260 DEG C in temperature of reaction, and reaction pressure is 1.0 ~ 8.0MPa, hydrogen ester mol ratio is 20 ~ 200: 1, and reaction velocity is 0.1 ~ 5 hour
-1condition under, raw material and catalyst exposure, reaction generates containing the effluent of ethylene glycol, and wherein, the transformation efficiency of barkite can be reached for 100%, and the selectivity of ethylene glycol can be greater than 95%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is reactor schematic diagram in the method for high efficiency production ethylene glycol of the present invention.
In Fig. 1,1 and 2 is feed(raw material)inlets, 3 is reactor upper covers, 4 is upper tubesheets, 5 is bundle of reaction tubes outer tubes, 6 is first subregion dividing plates, 7 is catalyst beds, 8 is reactor tank bodies, 9 is second subregion dividing plates, 10 is lower tubesheets, 11 is porous gas collection plates, 12 is product exit, 13 is collection chambers, 14 is reactor lower covers, 15 is the 3rd district's heat transferring medium entrances, 16 is the 3rd heat exchange blocks, 17 is the heat transferring medium outlets of the 3rd district, 18 is second district's heat transferring medium entrances, 19 is second heat exchange blocks, 20 is the heat transferring medium outlets of the secondth district, 21 is first district's heat transferring medium entrances, 22 is first heat exchange blocks, 23 is the heat transferring medium outlets of the firstth district, 24 is gas quadratic distribution rooms, 25 is reactor cover plates, 26 and 27 is gas distributing chamber, 28 is pipes in bundle of reaction tubes, 29 is inlet gas connecting hoses.
Fig. 1 Raw is introduced by feed(raw material)inlet 1 and 2, respectively through gas distributing chamber 26 and 27, pipe 28 in bundle of reaction tubes is introduced through inlet gas connecting hose 29, with enter in gas quadratic distribution room 24 after the reaction heat heat exchange in catalyst bed 7, enter in the catalyst bed 7 in bundle of reaction tubes outer tube 5 and bundle of reaction tubes between pipe 28 afterwards, react with catalyst exposure, after reacted product enters collection chamber 13, enter follow-up system through porous gas collection plate 11 by product exit 12.Enter in the catalyst bed 7 in bundle of reaction tubes outer tube 5 and bundle of reaction tubes between pipe 28 at reaction raw materials gas, with the reaction heat in catalyst exposure reaction process, successively through the first heat exchange block (22), second heat exchange block (19) and the 3rd heat exchange block (16), the temperature of each heat exchange block controls respectively by the temperature and flow etc. entering the heat transferring medium of each heat exchange block, in addition, unstripped gas is from pipe in bundle of reaction tubes 28 and reactant gases counter current contact process, also better promoter action is played to catalyst bed 7 heat balance, thus reach the uniform effect of whole reactor catalyst bed tempertaure.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take silicon oxide as carrier, according to total catalyst weight number meter, with 20 parts of Cu, the content of 5 parts of Bi and 2 part W preparation catalyzer, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 70 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=6 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add the silica sol binder making beating that silica support (specific surface area 150 meters squared per gram) and concentration are 10%; D () is shaping with double screw banded extruder, catalyzer is trifolium-shaped; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained catalyst A.
Take the catalyst A that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with dimethyl oxalate, is 220 DEG C in temperature of reaction, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is that under the condition of 2.8MPa, raw material contacts with catalyst A, and reaction generates the effluent containing ethylene glycol, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96%.
[embodiment 2]
According to each step and the condition of [embodiment 1], just its Support Silica average specific surface area is 280 meters squared per gram, and catalyst B obtained thus comprises 30 parts of Cu, 10 parts of Bi and 1 part W.
Take the catalyst B that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with dimethyl oxalate, is 250 DEG C in temperature of reaction, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 35% of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95%.
[embodiment 3]
According to each step and the condition of [embodiment 1], just its carrier is silicon oxide and aluminum oxide, and obtained catalyzer comprises 30 parts of Cu, and 3 parts of Bi and 15 part W, count catalyzer C.
Take the catalyzer C that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with oxalic acid diethyl ester, is 200 DEG C 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 ethylene glycol is 94%.
[embodiment 4]
According to each step and the condition of [embodiment 1], just its carrier is silicon oxide and aluminum oxide, and obtained catalyzer comprises 30 parts of Cu, and 2 parts of Bi and 8 part W, count catalyzer D.
Take the catalyzer D that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with oxalic acid diethyl ester, is 240 DEG C 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 ethylene glycol is 96%.
[embodiment 5]
According to each step and the condition of [embodiment 1], just its carrier is ZSM-5 molecular sieve, and obtained catalyzer composition comprises 45 parts of Cu, and 7 parts of Bi and 2 part W, count catalyzer E.
Take the catalyzer E that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with dimethyl oxalate, is 230 DEG C 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 ethylene glycol is 95%.
[embodiment 6]
According to each step and the condition of [embodiment 1], its carrier is silicon oxide, and obtained catalyzer composition comprises 20 parts of Cu, and 2 parts of Ba, count catalyzer F.
Take the catalyzer F that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature, the sleeve structure of inner and outer tubes is adopted to carry out heat exchange to catalyzer in addition, then being raw material with dimethyl oxalate, is 230 DEG C 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 mass percentage of dimethyl oxalate is under the condition of 14.5%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98%.
[comparative example 1]
According to condition and the catalyzer of [embodiment 1], just adopt insulation fix bed reactor, its reaction result is: the transformation efficiency of dimethyl oxalate is 98%, and the selectivity of ethylene glycol is 90%.
Claims (6)
1. a method for high efficiency production ethylene glycol take barkite as raw material, and with cupric or its oxide compound for catalyzer, be 170 ~ 270 DEG C in temperature of reaction, barkite weight space velocity is 0.2 ~ 5 hour
-1, hydrogen/ester mol ratio is 40 ~ 200: 1, reaction pressure is under 1.5 ~ 10MPa condition, raw material contacts with catalyst reactor, generate the effluent containing ethylene glycol, it is characterized in that, described reactor is subregion heat exchange and adopts the sleeve structure of inner and outer tubes catalyzer to be carried out to the shell-and-tube reactor of heat exchange, primarily of the first feed(raw material)inlet (1), second feed(raw material)inlet (2), first gas one time distributing chamber (26), second gas one time distributing chamber (27), gas quadratic distribution room (24), bundle of reaction tubes outer tube (5), pipe (28) in bundle of reaction tubes, catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product exit (12) composition, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22) according to reaction gas flow direction order, second heat exchange block (19) and the 3rd heat exchange block (16), first heat exchange block (22) and first district's heat transferring medium export (23) and are connected with first district's heat transferring medium entrance (21), second heat exchange block (19) exports (20) with second district's heat transferring medium entrance (8) with second district's heat transferring medium and is connected, and exports (17) be connected with the 3rd heat exchange block (16) with the 3rd district's heat transferring medium entrance (15) with the 3rd district's heat transferring medium, arrange pipe (28) in bundle of reaction tubes in catalyst bed (7), in bundle of reaction tubes, pipe (28) is connected with the first gas distributing chamber (26) and the second gas distributing chamber (27) in collection chamber (13) by inlet gas connecting hose (29), porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product exit (12), wherein, unstripped gas manages counter-current flow in (28) in bundle of reaction tubes.
2. the method for high efficiency production ethylene glycol according to claim 1, it is characterized in that reactor reaction temperature is 180 ~ 260 DEG C, barkite weight space velocity is 0.3 ~ 3 hour
-1, hydrogen/ester mol ratio is 50 ~ 150: 1, and reaction pressure is 2.0 ~ 6.0MPa.
3. the method for high efficiency production ethylene glycol according to claim 1, it is characterized in that in total catalyst weight number, the Cu and its oxides that catalyzer comprises 5 ~ 80 parts be active ingredient, 10 ~ 90 parts silicon oxide, at least one is carrier in molecular sieve or aluminum oxide, and the bismuth of 0.01 ~ 30 part and tungsten metallic element or its oxide compound are auxiliary agent.
4. the method for high efficiency production ethylene glycol according to claim 3, it is characterized in that in total catalyst weight number, the Cu and its oxides that catalyzer comprises 10 ~ 60 parts is active ingredient, at least one is carrier in the silicon oxide of 15 ~ 90 parts or aluminum oxide, and the bismuth of 0.05 ~ 20 part and tungsten metallic element or its oxide compound are auxiliary agent.
5. the method for high efficiency production ethylene glycol according to claim 1, it is characterized in that being separated by the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separated by the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).
6. the method for high efficiency production ethylene glycol is according to claim 1 1/8 ~ 1/3 of reactor length under it is characterized in that the first subregion dividing plate (6) distance reactor cover plate (25); Be 1/8 ~ 1/3 of reactor length under second subregion dividing plate (9) distance the first subregion dividing plate (6).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045625.6A CN102649695B (en) | 2011-02-25 | 2011-02-25 | High-efficiency production method for ethylene glycol |
| US14/001,120 US8962895B2 (en) | 2011-02-25 | 2012-02-24 | Method for the production of ethylene glycol |
| AU2012220219A AU2012220219B2 (en) | 2011-02-25 | 2012-02-24 | Ethylene glycol preparation method |
| PCT/CN2012/000237 WO2012113268A1 (en) | 2011-02-25 | 2012-02-24 | Ethylene glycol preparation method |
| MYPI2013701477A MY162972A (en) | 2011-02-25 | 2012-02-24 | Method for the production of ethylene glycol |
| RU2013143310/04A RU2570573C2 (en) | 2011-02-25 | 2012-02-24 | Method of producing ethylene glycol |
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| CN201110045625.6A CN102649695B (en) | 2011-02-25 | 2011-02-25 | High-efficiency production method for ethylene glycol |
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| CN103785415B (en) * | 2012-10-31 | 2016-03-30 | 中国石油化工股份有限公司 | Hydrogenation of carboxylic acids prepares the cobalt bismuth catalyst of alcohol |
| WO2017210614A1 (en) * | 2016-06-03 | 2017-12-07 | Iowa Corn Promotion Board | Continuous processes for the highly selective conversion of aldohexose-yielding carbohydrate to ethylene glycol |
| CN109225074B (en) * | 2018-09-30 | 2022-04-05 | 中石化宁波工程有限公司 | Temperature-variable isothermal shift reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
Non-Patent Citations (1)
| Title |
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| 草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性;黄维捷等;《工业催化》;20080630;第16卷(第6期);第13-17页 * |
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