CN102649706A - Method for preparing ethylene glycol through gas phase hydrogenation of oxalate - Google Patents
Method for preparing ethylene glycol through gas phase hydrogenation of oxalate Download PDFInfo
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- CN102649706A CN102649706A CN2011100471951A CN201110047195A CN102649706A CN 102649706 A CN102649706 A CN 102649706A CN 2011100471951 A CN2011100471951 A CN 2011100471951A CN 201110047195 A CN201110047195 A CN 201110047195A CN 102649706 A CN102649706 A CN 102649706A
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Abstract
The invention relates to a method for preparing ethylene glycol through gas phase hydrogenation of oxalate, and mainly solves the technical problem in the prior art that in the reaction process of hydrogenation of oxalate to ethylene glycol, the selectivity of ethylene glycol is low. The method adopts oxalate as the raw material and methanol, alcohol or water as a terminator, and comprises the step that the raw material is in contact with a copper bearing catalyst in a fluidized bed reactor of an external cyclone separator to generate an effluent containing ethylene glycol under the conditions that the reaction temperature is 170-270 DEG C, the weight space velocity of oxalate is 0.2-5hours <-1>, the hydrogen/ester molar ratio is 40-200:1 and the reaction pressure is 1.5-10MPa. By adopting the technical scheme, the problem is better solved, and the method provided by the invention can be used for industrial increase production of ethylene glycol.
Description
Technical field
The present invention relates to the method for a kind of barkite, particularly, be useful in the reaction process of hydrogenation of oxalate for preparing ethylene glycol about adopting the external placed type cyclonic separator through the gas phase hydrogenation preparing ethylene glycol.
Background technology
Terepthaloyl moietie (EG) is a kind of important Organic Chemicals; Be mainly used in to produce and gather vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc.; Can be used for industries such as coating, soup, brake fluid and printing ink in addition; Solvent and medium as ammonium pertorate are used to produce special solvent glycol ether etc., and purposes very extensively.
At present, China has surpassed the U.S. becomes the big terepthaloyl moietie consumption of the first in the world big country, and domestic apparent consumption average annual growth rate reached 17.4% in 2001～2006 years.Though China's terepthaloyl moietie throughput and increase of production are very fast,, all need a large amount of imports every year, and import volume is growing trend year by year because the powerful development of industry such as polyester still can not be satisfied the growing market requirement.
Current, the suitability for industrialized production of domestic and international large-scale terepthaloyl moietie all adopts the oxyethane direct hydration, i.e. the legal operational path of pressurized water, and production technology is monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC three companies basically.In addition, the research-and-development activity of the new synthetic technology of terepthaloyl moietie is also making progress always.Developed catalyzing epoxyethane hydration legal system terepthaloyl moietie production technology in succession like Shell company, UCC company, Moscow Mendelyeev chemical engineering institute, Oil of Shanghai Petrochemical Company institute etc.; Companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system terepthaloyl moietie production technology in succession; Companies such as Dow chemistry have developed EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
For reaction product water cut height, follow-up equipment (vaporizer) long flow path of direct hydration method, equipment is big, energy consumption is high, the process total recovery has only about 70%, directly influences the production cost of EG.Direct hydration method is compared with catalytic hydration and has been reduced the water ratio significantly, has obtained higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalytic hydration system EG replacement on-catalytic hydrating process is trend of the times so.No matter the technology that NSC 11801 (EC) legal system is equipped with EG aspect EO transformation efficiency, EG selectivity, still all has bigger advantage than EO direct hydration method aspect raw material, the energy expenditure, is a kind of method that maintains the leading position.EG and DMC co-production technology can make full use of the CO of oxidation of ethylene by-product
2Resource in existing EO production equipment, only needs to increase the reactions step of producing EC and just can produce two kinds of very value products, and is very attractive.
But the drawback of aforesaid method is to need the consumption of ethylene resource; And mainly lean on traditional petroleum resources refining for present ethene; And under the situation of following one section global oil price in period high-order operation for a long time; Replace oil production terepthaloyl moietie (non-petroleum path is the CO route again) with aboundresources, low-cost Sweet natural gas or coal, can possess the advantage of competing mutually with traditional ethene route.Wherein, synthetic gas synthesizes the EG new technology, may produce great influence to the innovation of EG production technique.With the carbon monoxide is the feedstock production dimethyl oxalate, is a very attractive Coal Chemical Industry route with preparation of ethanediol by dimethyl oxalate hydrogenation then.Now both at home and abroad to being that the research of feedstock production dimethyl oxalate has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparation of ethanediol by dimethyl oxalate hydrogenation, especially effectively improve the selectivity of terepthaloyl moietie and improve also not well breakthrough on the catalyst stability how.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol; It is active ingredient with the metallic copper, and zinc is auxiliary agent, adopts the coprecipitation method preparation; But this catalyzer barkite transformation efficiency is lower, and the selectivity of terepthaloyl moietie is lower simultaneously.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and the barkite transformation efficiency of this catalyzer and technology thereof is lower, and generally about 96%, the selectivity of terepthaloyl moietie is about about 92%.
Above-mentioned document related subject matter be that glycol selectivity is low.
Summary of the invention
Technical problem to be solved by this invention is to be used for the hydrogenation of oxalate for preparing ethylene glycol reaction process in the technical literature in the past, has the low technical problem of glycol selectivity, provides a kind of new barkite to pass through the method for gas phase hydrogenation preparing ethylene glycol.This method is used for the hydrogenation of oxalate for preparing ethylene glycol reaction process, has the high advantage of glycol selectivity.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of barkite is raw material through the method for gas phase hydrogenation preparing ethylene glycol with the barkite, is terminator with methyl alcohol, ethanol or water; In temperature of reaction is 170～270 ℃, and the 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 the interior copper containing catalyst of fluidized-bed reactor; Generation contains the elute of terepthaloyl moietie; Wherein fluidized-bed reactor is made up of settling vessel (5), stripper (11), interchanger (3) and external placed type cyclonic separator (8) basically, comprises emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divides device (6), gas tube (7), external placed type cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, and wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is the integral part on settling vessel (5) top, and its upper end links to each other with collection chamber (9) but do not communicate, and its lower end is positioned at outside the riser tube (4), zone of transition (B) outer upper ends; External placed type cyclonic separator (8) is positioned at settling vessel (5) outside, and its top inlet mouth links to each other with gas tube (7) top, and its air outlet communicates with collection chamber (9), and the dipleg of external placed type cyclonic separator (8) stretches in the negative area (C) of settling vessel (5); Collection chamber (9) is positioned at above the gas tube (7) and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1).
Preferred version is for being provided with terminator inlet 15 in the technique scheme near riser tube 4 lower regions, and terminator inlet 15 is 0～4/5 of riser tube 4 height apart from the vertical range of riser tube 4 bottoms; Terminator inlet 15 distributes along riser tube 4 lower regions ringwise; The internal diameter of riser tube 4 is 1/15～1/2 of emulsion zone A external diameters, and the height of riser tube 4 is 1/5～5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10～1/2 of emulsion zone A vertical height with emulsion zone A communication port apart from emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20～1/2 of an emulsion zone A vertical height.
Optimizing reaction conditions in the technique scheme is: temperature of reaction is 180～250 ℃, and the barkite weight space velocity is 0.2～3 hour
-1, hydrogen/ester mol ratio is 40～100: 1, and reaction pressure is 1.5～5MPa, and support of the catalyst is preferably selected from least a in silicon oxide or the aluminum oxide, and the average preferable range of granules of catalyst diameter is 30～180 microns.
As everyone knows, hydrogenation of oxalate for preparing ethylene glycol reaction is thermopositive reaction, and the hydrogenation of oxalate for preparing ethylene glycol reaction is cascade reaction, and terepthaloyl moietie is the intermediate product of reaction process, if excessive hydrogenation can generate ethanol.Research is also found; The best speech " form " of hydrogenation of oxalate for preparing ethylene glycol reaction is very narrow, and temperature low reaction transformation efficiency is low, and the selectivity of terepthaloyl moietie was low when temperature was high; Control reaction bed uniformity of temperature profile is most important; The temperature distribution of beds is even more, and the selection of terepthaloyl moietie is control more easily just, and keep higher selectivity easily.Adopt fluidized-bed reactor among the present invention, make full use of fluidized-bed reactor and conduct heat evenly, and the characteristics of uniformity of temperature profile, guarantee that the selectivity of terepthaloyl moietie is higher.Research is also found to adopt in the hydrogenation of oxalate for preparing ethylene glycol fluidized-bed reaction process; Under raw material and the catalyzer Long contact time situation; Still can continue to transform, especially at the settling zone of hydrogenation of oxalate for preparing ethylene glycol fluidized-bed reactor, a large amount of unsegregated catalyzer can continue to react under the condition of high temperature; Cause the barkite rate of loss high, glycol selectivity is low.The present invention also injects terminator through the zone, outlet position of leaving catalytic bed in catalyzer and reaction product; On the one hand, the terminator that temperature is lower contacts with pyroreaction mixture and catalyzer, can significantly reduce the temperature of reaction mixture and catalyzer; This can further quicken the rapid temperature-fall period of pyroreaction mixture and catalyzer; After reaction mixture that temperature sharply reduces and catalyzer left reaction zone, side reaction was few, and it is little to continue the reaction odds; Reduce the rate of loss of raw material, improved the selectivity of terepthaloyl moietie.
The present invention uses device shown in Figure 1, adopts the copper oxide fluid catalyst, and methyl alcohol, ethanol or water are terminator, are raw material with the barkite, are 170～270 ℃ in temperature of reaction, and the 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 the interior copper containing catalyst of fluidized-bed reactor; Generation contains the elute of terepthaloyl moietie, and its result is that the transformation efficiency of barkite can be reached for 100%; The selectivity of terepthaloyl moietie can obtain better technical effect greater than 98%.
Description of drawings
Fig. 1 is the fluidized-bed reactor synoptic diagram that the present invention adopted.
A is that emulsion zone, B are that zone of transition, C are negative areas, the 1st among Fig. 1, material inlet, the 2nd, sparger or grid distributor, the 3rd, interchanger, the 4th, riser tube; The 5th, settling vessel, the 6th, divide device soon, the 7th, gas tube, the 8th, external placed type cyclonic separator; The 9th, collection chamber, the outlet of 10 product gas, the 11st, stripper, the 12nd, regenerator sloped tube; The 13rd, inclined tube to be generated, the 14th, stripped vapor inlet, the 15th, terminator inlet.
Raw material is introduced by material inlet 1 among Fig. 1, and through gas distributor or grid distributor 2 laggard emulsion zone A and the catalyzer contact reacts of going into fluidized-bed that distribute, catalyzer and reaction mixture are through zone of transition B entering riser tube 4; Behind vortex quick separation device 6 sharp separation of riser tube 4 upper ends (end); Most of catalyzer gets into the lower region of settling vessel C; The part catalyzer that reaction mixture is carried secretly gets into through gas tube 7 and carries out secondary separation through external placed type cyclonic separator 8; Product gas after the separation gets into collection chamber 9 through the outlet of external placed type cyclonic separator 8, is drawn by product gas outlet 10.Return the lower region of settling vessel 5 through the dipleg of external placed type cyclonic separator 8 from the catalyzer after 8 separation of external placed type cyclonic separator.The reclaimable catalyst of the C bottom, negative area in the settling vessel 5 gets into stripper 11; Behind stripped vapor stripping from stripped vapor inlet 14; Get into revivifier (revivifier omits among the figure) through inclined tube 12 to be generated, regenerator gets into the fluidized-bed reactor emulsion zone A of hydrogenation of oxalate for preparing ethylene glycol through regenerator sloped tube 12.In addition, the part catalyzer in the settling vessel 5 gets into the fluidized-bed reactor emulsion zone A bottom of hydrogenation of oxalate for preparing ethylene glycol and continues reaction with catalyst mix after interchanger 3 heat exchange, and whole process circulation is carried out.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/5 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/10 of an emulsion zone external diameter, and the height of riser tube is 1/4 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/5 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, and the vertical height of fluidized-bed reactor zone of transition is 1/10 of an emulsion zone vertical height.80 microns of its particle diameter average out to adopt to consist of 30wt%Cu+10wt%Zn+1wt%W/SiO
2Fluid catalyst, methyl alcohol is terminator, uses dimethyl oxalate to be raw material, the weight ratio of raw material and terminator is 10: 1, the terminator feeding temperature is 40 ℃, is 240 ℃ in temperature of reaction, weight space velocity is 1 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 98.6%.
[embodiment 2]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/8 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/12 of an emulsion zone external diameter, and the height of riser tube is 1/2 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/3 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, and the vertical height of fluidized-bed reactor zone of transition is 1/5 of an emulsion zone vertical height.Employing consists of 40wt%Cu+5wt%Zn+1wt%Ni/SiO
2Fluid catalyst, 100 microns of its particle diameter average out to, ethanol is terminator, uses oxalic acid diethyl ester to be raw material, the weight ratio of raw material and terminator is 10: 1, the terminator feeding temperature is 40 ℃, is 220 ℃ in temperature of reaction, weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.0MPa, and the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of terepthaloyl moietie is 97.9%.
[embodiment 3]
With the fluidized-bed reactor of Fig. 1, adopt to consist of 28wt%Cu+3wt%Al/SiO
2Fluid catalyst; 120 microns of granules of catalyst diameter average out to, water are terminator, and the terminator inlet is 1/10 of a riser tube length apart from the vertical range of riser tube bottom; The internal diameter of riser tube is 1/6 of an emulsion zone external diameter, and the height of riser tube is 1/8 of an emulsion zone height.Regenerator sloped tube and emulsion zone communication port are 1/6 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance.The vertical height of zone of transition is 1/7 of an emulsion zone vertical height.Distance set air chamber top, the gas inlet vertical range of cyclonic separator is 1/4 of a settling vessel diameter.Use dimethyl oxalate to be raw material, the weight ratio of raw material and terminator is 40: 1, and the terminator feeding temperature is 35 ℃, is 220 ℃ in temperature of reaction, and weight space velocity is 1.2 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 2.8MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 98.3%.
[embodiment 4]
With the fluidized-bed reactor of Fig. 1, adopt to consist of 25wt%Cu+3wt%Ni/SiO
2Fluid catalyst; 110 microns of granules of catalyst diameter average out to, methyl alcohol are terminator, and the terminator inlet is 1/5 of a riser tube length apart from the vertical range of riser tube bottom; The internal diameter of riser tube is 1/4 of an emulsion zone external diameter, and the height of riser tube is 1/8 of an emulsion zone height.Regenerator sloped tube and emulsion zone communication port are 1/10 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance.The vertical height of zone of transition is 1/6 of an emulsion zone vertical height.Distance set air chamber top, the gas inlet vertical range of cyclonic separator is 1/6 of a settling vessel diameter.Use dimethyl oxalate to be raw material, the weight ratio of raw material and terminator is 60: 1, and the terminator feeding temperature is 25 ℃, is 190 ℃ in temperature of reaction, and weight space velocity is 0.4 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 99.8%, and the selectivity of terepthaloyl moietie is 98.8%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just the reactor drum of hydrogenation of oxalate for preparing ethylene glycol adopts fixed-bed reactor, and does not add terminator, and reaction result is: the transformation efficiency of dimethyl oxalate is 96.5%, and the selectivity of terepthaloyl moietie is 91.2%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just the reactor drum of hydrogenation of oxalate for preparing ethylene glycol adopts fixed-bed reactor, and does not add terminator, and reaction result is: the transformation efficiency of oxalic acid diethyl ester is 95.4%, and the selectivity of terepthaloyl moietie is 90.3%.
Claims (8)
1. a barkite is raw material through the method for gas phase hydrogenation preparing ethylene glycol with the barkite, is terminator with methyl alcohol, ethanol or water, is 170～270 ℃ in temperature of reaction, and the 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 the interior copper containing catalyst of fluidized-bed reactor; Generation contains the elute of terepthaloyl moietie; Wherein fluidized-bed reactor is made up of settling vessel (5), stripper (11), interchanger (3) and external placed type cyclonic separator (8) basically, comprises emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divides device (6), gas tube (7), external placed type cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, and wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is the integral part on settling vessel (5) top, and its upper end links to each other with collection chamber (9) but do not communicate, and its lower end is positioned at outside the riser tube (4), zone of transition (B) outer upper ends; External placed type cyclonic separator (8) is positioned at settling vessel (5) outside, and its top inlet mouth links to each other with gas tube (7) top, and its air outlet communicates with collection chamber (9), and the dipleg of external placed type cyclonic separator (8) stretches in the negative area (C) of settling vessel (5); Collection chamber (9) is positioned at above the gas tube (7) and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1).
2. according to the method for the said barkite of claim 1, it is characterized in that near riser tube (4) lower region, terminator inlet (15) being set through the gas phase hydrogenation preparing ethylene glycol.
3. according to the method for the said barkite of claim 1, it is characterized in that terminator inlet (15) is 0～4/5 of riser tube (a 4) length apart from the vertical range of riser tube (4) bottom through the gas phase hydrogenation preparing ethylene glycol.
4. according to the method for the said barkite of claim 1, it is characterized in that terminator inlet (15) distributes along riser tube (4) lower region ringwise through the gas phase hydrogenation preparing ethylene glycol.
5. according to the method for the said barkite of claim 1 through the gas phase hydrogenation preparing ethylene glycol, the internal diameter that it is characterized in that riser tube (4) is 1/15～1/2 of emulsion zone (A) external diameter, and the height of riser tube (4) is 1/5～5/1 of emulsion zone (A) height.
6. according to the method for the said barkite of claim 1, it is characterized in that regenerator sloped tube (12) and emulsion zone (A) communication port are 1/10～1/2 of emulsion zone (A) vertical heights apart from emulsion zone (A) bottom vertical distance through the gas phase hydrogenation preparing ethylene glycol.
7. according to the method for the said barkite of claim 1 through the gas phase hydrogenation preparing ethylene glycol, the vertical height that it is characterized in that zone of transition (B) is 1/20～1/2 of emulsion zone (A) vertical height.
8. according to the method for the said barkite of claim 1 through the gas phase hydrogenation preparing ethylene glycol, it is characterized in that temperature of reaction is 180～250 ℃, the barkite weight space velocity is 0.2～3 hour
-1, hydrogen/ester mol ratio is 40～100: 1, and reaction pressure is 1.5～5MPa, and support of the catalyst is selected from least a in silicon oxide or the aluminum oxide, 30～180 microns of granules of catalyst diameter average out to.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105478175A (en) * | 2015-12-27 | 2016-04-13 | 安徽淮化股份有限公司 | Catalyst regeneration system suitable for hydrogenation reaction for preparing ethylene glycol from synthesis gas |
| CN106861710A (en) * | 2017-02-20 | 2017-06-20 | 宁波中科远东催化工程技术有限公司 | Catalyst of dimethyl oxalate preparing ethylene glycol and preparation method thereof |
| CN106928021A (en) * | 2017-02-20 | 2017-07-07 | 宁波中科远东催化工程技术有限公司 | A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| WO2021047051A1 (en) * | 2019-09-12 | 2021-03-18 | 南京延长反应技术研究院有限公司 | Reaction system and process for enhancing hydrogenation of dimethyl oxalate during preparation of ethylene glycol from coal |
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| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478175A (en) * | 2015-12-27 | 2016-04-13 | 安徽淮化股份有限公司 | Catalyst regeneration system suitable for hydrogenation reaction for preparing ethylene glycol from synthesis gas |
| CN105478175B (en) * | 2015-12-27 | 2018-01-16 | 安徽淮化股份有限公司 | A kind of catalyst regeneration system suitable for synthesis gas preparing ethylene glycol hydrogenation reaction |
| CN106861710A (en) * | 2017-02-20 | 2017-06-20 | 宁波中科远东催化工程技术有限公司 | Catalyst of dimethyl oxalate preparing ethylene glycol and preparation method thereof |
| CN106928021A (en) * | 2017-02-20 | 2017-07-07 | 宁波中科远东催化工程技术有限公司 | A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN106928021B (en) * | 2017-02-20 | 2020-04-24 | 宁波中科远东催化工程技术有限公司 | Method for preparing ethylene glycol by dimethyl oxalate hydrogenation |
| WO2021047051A1 (en) * | 2019-09-12 | 2021-03-18 | 南京延长反应技术研究院有限公司 | Reaction system and process for enhancing hydrogenation of dimethyl oxalate during preparation of ethylene glycol from coal |
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| CN102649706B (en) | 2015-04-08 |
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