CN102649699A - Method for preparing ethylene glycol through catalytic hydrogenation reaction by oxalic ester - Google Patents
Method for preparing ethylene glycol through catalytic hydrogenation reaction by oxalic ester Download PDFInfo
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- CN102649699A CN102649699A CN2011100463616A CN201110046361A CN102649699A CN 102649699 A CN102649699 A CN 102649699A CN 2011100463616 A CN2011100463616 A CN 2011100463616A CN 201110046361 A CN201110046361 A CN 201110046361A CN 102649699 A CN102649699 A CN 102649699A
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Abstract
The invention relates to a method for preparing ethylene glycol through the catalytic hydrogenation reaction by oxalic ester, and mainly solves the technical problem in the prior art that during the process of preparing ethylene glycol through hydrogenation by oxalic ester, the selectivity of ethylene glycol is low. Through the adoption of the technical scheme that oxalic ester is taken as a raw material, 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 a copper-contained catalyst in a multi-zone heat exchanging pipe reactor, an ethylene glycol contained effluent is generated, and the invention solves the problem of low selectivity of ethylene glycol well, and can be used in the industrial production of preparing ethylene glycol through hydrogenation by oxalic ester.
Description
Technical field
The present invention and a kind of barkite particularly about adopting subregion heat exchanging pipe reactor drum to realize the reaction of hydrogenation of oxalate for preparing ethylene glycol, are useful in the hydrogenation of oxalate for preparing ethylene glycol reaction process through the method for catalytic hydrogenation reaction 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 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%.
The subject matter that the related technology of above-mentioned document exists is that feed stock conversion is low, and 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, and the technical problem that the purpose selectivity of product is low provides a kind of new barkite to pass through the method for catalytic hydrogenation reaction preparing ethylene glycol.This method is used for barkite through shortening preparing ethylene glycol process, has the high advantage of ethylene glycol product 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 catalytic hydrogenation reaction preparing ethylene glycol with the barkite, 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 multi-region heat exchanging pipe reactor drum; Generation contains the elute of terepthaloyl moietie, and wherein multi-region heat exchanging pipe reactor drum is made up of feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product outlet (12) basically, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) in proper order according to the mobile direction of reaction gas; The first heat exchange block (22) links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16).
Porous gas sparger (2) is positioned at gas distribution chamber (24) in the technique scheme, and is connected with feed(raw material)inlet (1), and porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer to be heat transferring medium.Separate through the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).The first subregion dividing plate (6) is following apart from reactor drum upper tubesheet (4) to be 1/8～1/3 of reactor length; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 190～260 ℃, and the barkite weight space velocity is 0.4～2 hour
-1, hydrogen/ester mol ratio is 40～100: 1, reaction pressure is 1.5～5MPa.
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 optimum response " 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.For the fixed-bed reactor of routine, because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor drum is anterior from balanced remote; Speed of response is fast, and it is also many to emit reaction heat, the rear portion with reaction near balance; Speed of response slows down, and emits reaction heat and also lacks, if the same before and after the temperature of refrigerant; If reduce coolant temperature like this, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of top or anterior high speed of response and strong reaction heat; Then reactor lower part or rear portion reaction heat reduce; Move heat and cause temperature of reaction to descend, speed of response is further slowed down below catalyst activity with regard to stopped reaction, therefore be difficult to the way that makes the best of both worlds of accomplishing that the front and rear part reaction is all carried out under optimal reaction temperature greater than reaction heat.The present invention is directed to this fundamental contradiction, break through existing refrigerant, and adopt the different sections of reactor drum to adopt the differing temps refrigerant to solve with same temperature; Make the size that heat exchange is shifted out by reaction heat in the reaction need design; A plurality of districts before and after specifically can being divided in proper order by reaction gas flow direction in catalyst layer come indirect heat exchange by refrigerant through heat transfer tube, thereby realize the equiblibrium mass distribution of full bed temperature; This is for the efficient of maximized performance catalyzer; Farthest reduce the loss of barkite, improve the selectivity of terepthaloyl moietie, useful effect is provided.
The present invention uses device shown in Figure 1, adopts the subregion heat exchange, and accurately controlled temperature adopts the copper oxide catalyzer, is raw material with the barkite, is 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 multi-region heat exchanging pipe reactor drum; Generation contains the elute of terepthaloyl moietie, and wherein, the transformation efficiency of barkite can be reached for 100%; The selectivity of terepthaloyl moietie can obtain better technical effect greater than 97%.
Description of drawings
The reactor drum synoptic diagram that Fig. 1 adopts for the present invention.
1 is the feed(raw material)inlet among Fig. 1, the 2nd, and porous gas sparger, the 3rd, reactor drum upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes; 6 is first subregion dividing plates, the 7th, and catalyst bed, the 8th, the reactor drum tank body, 9 is second subregion dividing plates; The 10th, lower tubesheet, the 11st, porous gas collection plate, the 12nd, product outlet, the 13rd, collection chamber; The 14th, the reactor drum lower cover, 15 is the 3rd district's heat transferring medium inlets, and 16 is the 3rd heat exchange blocks, and 17 is the heat transferring medium outlets of the 3rd district; 18 is second district's heat transferring medium inlets, and 19 is second heat exchange blocks, and 20 is the heat transferring medium outlets of second district, and 21 is first district's heat transferring medium inlets; 22 is first heat exchange blocks, and 23 is the heat transferring medium outlets of first district, the 24th, and the gas distribution chamber
Raw material is introduced by feed(raw material)inlet 1 among Fig. 1;, porous gas sparger 2 gets into gas distribution chamber 24 after distributing; Get in the bundle of reaction tubes 5 afterwards and catalyst bed 7 contact reactss; The heat that produces in the reaction process is taken away through bundle of reaction tubes 5 outer heat transferring mediums, and reacted gas gets into collection chamber 13, gets into follow-up systems through porous gas collection plate 11 after product exports 12 then.In reaction raw materials gas gets into bundle of reaction tubes 5 and in the catalyst bed 7 contact reacts processes; Successively through the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16); The temperature of each heat exchange block can be through getting into each heat exchange block the controls respectively such as temperature and flow of heat transferring medium, thereby reach the effect that temperature all goes on foot.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With reactor drum shown in Figure 1, it is a multi-region heat exchanging pipe reactor drum, and wherein the first subregion dividing plate is following apart from the reactor drum upper tubesheet is 1/4 of reactor length; Second subregion dividing plate distance, the first subregion dividing plate is 1/6 of reactor length down.Its first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thereby the control of realization response device catalyst bed temperature adopts quality group to become 30wt%Cu+10wt%Bi+1wt%W/SiO
2Copper catalyst, use dimethyl oxalate to be raw material, be 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 96.9%.
[embodiment 2]
With reactor drum shown in Figure 1, it is a multi-region heat exchanging pipe reactor drum, and wherein the first subregion dividing plate is following apart from the reactor drum upper tubesheet is 1/7 of reactor length; Second subregion dividing plate distance, the first subregion dividing plate is 1/4 of reactor length down.Its first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thereby the control of realization response device catalyst bed temperature adopts quality group to become 30wt%Cu+10wt%Zn+1wt%Ni/SiO
2Copper catalyst, use oxalic acid diethyl ester to be raw material, be 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 96.8%.
[embodiment 3]
With reactor drum shown in Figure 1, it is a multi-region heat exchanging pipe reactor drum, and wherein the first subregion dividing plate is following apart from the reactor drum upper tubesheet is 1/4 of reactor length; Second subregion dividing plate distance, the first subregion dividing plate is 1/6 of reactor length down.Its first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thereby the control of realization response device catalyst bed temperature adopts quality group to become 40wt%Cu+10wt%Zn/SiO
2Copper catalyst, use dimethyl oxalate to be raw material, be 180 ℃ in temperature of reaction, weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 2.5MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 98.2%.
[embodiment 4]
With reactor drum shown in Figure 1, it is a multi-region heat exchanging pipe reactor drum, and wherein the first subregion dividing plate is following apart from the reactor drum upper tubesheet is 1/4 of reactor length; Second subregion dividing plate distance, the first subregion dividing plate is 1/6 of reactor length down.Its first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thereby the control of realization response device catalyst bed temperature adopts quality group to become 25wt%Cu+1wt%Ni+0.3wt%Co/SiO
2Copper catalyst, use dimethyl oxalate to be raw material, be 210 ℃ in temperature of reaction, weight space velocity is 0.8 hour
-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 97.5%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just reactor drum adopts insulation fix bed reactor, and reaction result is: the transformation efficiency of dimethyl oxalate is 96.5%, and the selectivity of terepthaloyl moietie is 90.2%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just reactor drum adopts insulation fix bed reactor, and reaction result is: the transformation efficiency of oxalic acid diethyl ester is 95.4%, and the selectivity of terepthaloyl moietie is 89.3%.
Claims (6)
1. a barkite is raw material through the method for catalytic hydrogenation reaction preparing ethylene glycol with the barkite, 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 multi-region heat exchanging pipe reactor drum; Generation contains the elute of terepthaloyl moietie, and wherein multi-region heat exchanging pipe reactor drum is made up of feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product outlet (12) basically, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) in proper order according to the mobile direction of reaction gas; The first heat exchange block (22) links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16).
2. according to the method for the said barkite of claim 1 through the catalytic hydrogenation reaction preparing ethylene glycol; The porous gas sparger (2) that it is characterized in that multi-region heat exchanging pipe reactor drum is positioned at gas distribution chamber (24); And be connected with feed(raw material)inlet (1); Porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).
3. according to the method for the said barkite of claim 1 through the catalytic hydrogenation reaction preparing ethylene glycol, it is characterized in that catalyst bed (7) is positioned at bundle of reaction tubes (5), bundle of reaction tubes (5) is outer to be heat transferring medium.
4. according to the method for the said barkite of claim 1 through the catalytic hydrogenation reaction preparing ethylene glycol; It is characterized in that separating through the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).
5. according to the method for the said barkite of claim 1 through the catalytic hydrogenation reaction preparing ethylene glycol, it is characterized in that the first subregion dividing plate (6) following apart from reactor drum upper tubesheet (4) be 1/8～1/3 of reactor length; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
6. according to the method for the said barkite of claim 1 through the catalytic hydrogenation reaction preparing ethylene glycol, it is characterized in that temperature of reaction is 190～260 ℃, the barkite weight space velocity is 0.4～2 hour
-1, hydrogen/ester mol ratio is 40～100: 1, reaction pressure is 1.5～5MPa.
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| CN201110046361.6A CN102649699B (en) | 2011-02-25 | 2011-02-25 | Method for preparing ethylene glycol through catalytic hydrogenation reaction by oxalic ester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043457A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Catalyst and method for preparation of glycol by oxalate hydrogenation |
| CN106588661A (en) * | 2015-10-16 | 2017-04-26 | 中国石化扬子石油化工有限公司 | Method for preparing glycolate through catalytic hydrogenation reaction of oxalate |
| CN109400443A (en) * | 2018-12-18 | 2019-03-01 | 中触媒新材料股份有限公司 | A kind of device and method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
Citations (1)
| 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 |
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2011
- 2011-02-25 CN CN201110046361.6A patent/CN102649699B/en active Active
Patent Citations (1)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 黄维捷等: "草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性", 《工业催化》, vol. 16, no. 6, 30 June 2008 (2008-06-30), pages 13 - 17 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043457A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Catalyst and method for preparation of glycol by oxalate hydrogenation |
| CN106588661A (en) * | 2015-10-16 | 2017-04-26 | 中国石化扬子石油化工有限公司 | Method for preparing glycolate through catalytic hydrogenation reaction of oxalate |
| CN109400443A (en) * | 2018-12-18 | 2019-03-01 | 中触媒新材料股份有限公司 | A kind of device and method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN109400443B (en) * | 2018-12-18 | 2024-02-27 | 中触媒新材料股份有限公司 | Device and method for preparing ethylene glycol through dimethyl oxalate hydrogenation |
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