CN102649698A - High-efficiency production method for ethylene glycol - Google Patents
High-efficiency production method for ethylene glycol Download PDFInfo
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- CN102649698A CN102649698A CN2011100463531A CN201110046353A CN102649698A CN 102649698 A CN102649698 A CN 102649698A CN 2011100463531 A CN2011100463531 A CN 2011100463531A CN 201110046353 A CN201110046353 A CN 201110046353A CN 102649698 A CN102649698 A CN 102649698A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a high-efficiency production method for ethylene glycol, and mainly solves the technical problem of 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, 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 efficient production method of terepthaloyl moietie, particularly about adopting subregion heat exchanging pipe reactor drum to realize that dimethyl oxalate or oxalic acid diethyl ester hydrogenation generate the method for terepthaloyl moietie.
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.
2010 27 volumes of document " spectrographic laboratory ", 2 phase 616-619 pages or leaves disclose the research of one piece of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen, and it has prepared Cu-B/ γ-Al through the chemical reduction sedimentation
2O
3, Cu-B/SiO
2Amorphous alloy catalyst, its evaluation result show, 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 technology thereof is lower, and generally about 96%, the selectivity of terepthaloyl moietie is about about 92%.
The subject matter that above-mentioned document exists is that glycol selectivity is lower, remains further to improve and improve.
Summary of the invention
Technical problem to be solved by this invention is the low problem of glycol selectivity that in the past exists in the technology.A kind of efficient production method of new terepthaloyl moietie is provided.This method 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 efficient production method of terepthaloyl moietie is a raw material with the barkite, is catalyzer with cupric or its oxide compound; In temperature of reaction is 170～270 ℃, and the barkite weight space velocity is 0.2～5 hour
-1, hydrogen/ester mol ratio is 40～200: 1, and reaction pressure is under 1.5～10MPa condition, and raw material contacts with catalyst reactor, generates the elute that contains terepthaloyl moietie, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
The reaction conditions of reactor drum is preferably in the technique scheme: temperature of reaction is 180～260 ℃, and the barkite weight space velocity is 0.3～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1, reaction pressure is 2.0～6.0MPa.The catalyzer preferred version is in the total catalyst weight umber; Catalyzer comprises that 5～80 parts copper and oxide compound thereof are at least aly in active ingredient, 10～90 parts silicon oxide, molecular sieve or the aluminum oxide to be carrier, and 0.01～30 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent.Catalyzer more preferably scheme in the total catalyst weight umber; Catalyzer comprises that 10～60 parts copper and oxide compound thereof are at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent.
The reactor drum of inventive method mainly 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) in the technique scheme, 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), 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.
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, and speed of response is fast; It is also many to emit reaction heat, and near balance, speed of response slows down with reaction at the rear portion; It is also few to emit reaction heat, 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, and move heat and cause temperature of reaction to descend greater than reaction heat; 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.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 high-efficiency method for producing of terepthaloyl moietie of the present invention adopts device shown in Figure 1, adopts the subregion heat exchange; Accurately controlled temperature adopts the copper oxide catalyzer, is raw material with the barkite; In temperature of reaction is 160～260 ℃; Reaction pressure is 1.0～8.0MPa, and the hydrogen ester mol ratio is 20～200: 1, and reaction velocity is 0.1～5 hour
-1Condition under, raw material contacts with catalyzer, reaction generates the elute contain terepthaloyl moietie, wherein, the transformation efficiency of barkite can be reached for 100%, the selectivity of terepthaloyl moietie can obtain better technical effect greater than 95%.
Description of drawings
Fig. 1 is reactor drum synoptic diagram in the efficient production method of terepthaloyl moietie of 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, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
According to the content preparation catalyzer of the silicon oxide of 20wt%Cu+5wt%Bi+2wt%W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 70 ℃ of following co-precipitation, pH=6 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding silica support (specific surface area 150 meters squared per gram) and concentration are 10% silica sol binder making beating; (d) with the moulding of twin screw banded extruder, catalyzer is trifolium-shaped; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make catalyst A.
Take by weighing the catalyst A that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the dimethyl oxalate; In temperature of reaction is 220 ℃, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 2.8MPa, and raw material contacts with catalyst A, and reaction generates the elute that contains terepthaloyl moietie, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 94.3%.
[embodiment 2]
According to each step and the condition of [embodiment 1], just its carrier average specific surface area is 280 meters squared per gram, and the catalyst B that makes thus is 30wt%Cu+10wt%Bi+1wt%W and surplus silicon oxide.Take by weighing the catalyst B that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the dimethyl oxalate; In temperature of reaction is 250 ℃, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is that the transformation efficiency of dimethyl oxalate is 100% under 35% the condition of 3.0MPa, and the selectivity of terepthaloyl moietie is 95.6%.
[embodiment 3]
Press the silicon oxide of 40wt%Cu+3wt%Bi+15wt%W and surplus and the content preparation catalyzer of aluminum oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, pH=7 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding alumina supporter (specific surface area 300 meters squared per gram) and concentration are 15% silica sol binder making beating; (d) with the moulding of twin screw banded extruder, catalyzer is trifolium-shaped; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make catalyzer C.
Take by weighing the catalyzer C that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the oxalic acid diethyl ester; In temperature of reaction is 200 ℃, 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 terepthaloyl moietie is 93.8%.
[embodiment 4]
Press the silicon oxide of 30wt%Cu+1wt%Bi+8wt%W and surplus and the content preparation catalyzer of aluminum oxide, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, pH=7 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+Back adding alumina supporter (specific surface area 100 meters squared per gram) and concentration are 6% silica sol binder making beating; (d) with the moulding of twin screw banded extruder, catalyzer is trifolium-shaped; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make catalyzer D.
Take by weighing the catalyzer D that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the oxalic acid diethyl ester; In temperature of reaction is 240 ℃, 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 100%, and the selectivity of terepthaloyl moietie is 94.1%.
[embodiment 5]
Press the content preparation catalyzer of the ZSM-5 molecular sieve of 45wt%Cu+8wt%Bi+2wt%W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, pH=5 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific surface area 450 meters squared per gram) making beating; (d) with the moulding of twin screw banded extruder, catalyzer is trifolium-shaped; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make catalyzer E.
Take by weighing the catalyzer E that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the dimethyl oxalate; In temperature of reaction is 230 ℃, 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 terepthaloyl moietie is 97.4%.
[embodiment 6]
Press the content preparation catalyzer of the ZSM-5 molecular sieve of 25wt%Cu+0.8wt%Bi+4wt%W and surplus, its step is following: (a) mixed nitrate solution and the sodium carbonate solution of copper, bismuth and the tungsten of configuration desired concn; (b) above-mentioned solution constantly stirs in the precipitation process 65 ℃ of following co-precipitation, pH=5 when deposition stops; (c) above-mentioned deposition slurries are used the deionized water repetitive scrubbing, until no Na
+The back adds ZSM-5 molecular sieve carrier (specific surface area 400 meters squared per gram) making beating; (d) with the moulding of twin screw banded extruder, catalyzer is trifolium-shaped; (e) 120 ℃ of dryings are 6 hours, 450 ℃ of following roastings 4 hours.Promptly make catalyzer.
Take by weighing the catalyzer F that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure; Realize the difference of temperature, thereby the control of realization response device catalyst bed temperature is raw material then with the dimethyl oxalate; In temperature of reaction is 230 ℃, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is 2.8MPa, and the quality percentage composition of dimethyl oxalate is that the transformation efficiency of dimethyl oxalate is 100% under 14.5% the condition, and the selectivity of terepthaloyl moietie is 98.1%.
[comparative example 1]
Accompanying drawing 1 shown device is adopted in test, and condition and catalyzer according to [embodiment 1] just only adopt the adiabatic fixed-bed reactor, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 91.2%.
Claims (8)
1. the efficient production method of a terepthaloyl moietie is a raw material with the barkite, is catalyzer with cupric or its oxide compound, 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, and reaction pressure is under 1.5～10MPa condition, and raw material contacts with catalyst reactor, generates the elute that contains terepthaloyl moietie, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
2. according to the efficient production method of the said terepthaloyl moietie of claim 1, it is characterized in that the reactor reaction temperature is 180～260 ℃, the barkite weight space velocity is 0.3～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1, reaction pressure is 2.0～6.0MPa.
3. according to the efficient production method of the said terepthaloyl moietie of claim 1; It is characterized in that in the total catalyst weight umber; Catalyzer comprises that 5～80 parts copper and oxide compound thereof are at least aly in active ingredient, 10～90 parts silicon oxide, molecular sieve or the aluminum oxide to be carrier, and 0.01～30 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent.
4. according to the efficient production method of the said terepthaloyl moietie of claim 3; It is characterized in that in the total catalyst weight umber; Catalyzer comprises that 10～60 parts copper and oxide compound thereof are at least aly in active ingredient, 15～90 parts silicon oxide or the aluminum oxide to be carrier, and 0.05～20 part bismuth and tungsten metallic element or its oxide compound are auxiliary agent.
5. according to the efficient production method of the said terepthaloyl moietie of claim 1; It is characterized in that reactor drum mainly exports (12) by 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 and forms, 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).
6. according to the efficient production method of the said terepthaloyl moietie of claim 1; It is characterized in that reactor drum porous gas sparger (2) 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); Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer to be heat transferring medium.
7. according to the efficient production method of the said terepthaloyl moietie of claim 5; It is characterized in that separating through the first subregion dividing plate (6) between the reactor drum 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).
8. according to the efficient production method of the said terepthaloyl moietie of claim 7, it is characterized in that the reactor drum first subregion dividing plate (6) is 1/8～1/3 of reactor length apart from reactor drum upper tubesheet (4) is following; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110627289A (en) * | 2019-10-28 | 2019-12-31 | 中国华电科工集团有限公司 | Low-temperature flue gas heating wastewater concentration system |
| CN110746024A (en) * | 2019-10-28 | 2020-02-04 | 中国华电科工集团有限公司 | Concentrated waste heat retrieval and utilization device of low temperature economizer waste water |
| CN111517916A (en) * | 2019-02-02 | 2020-08-11 | 航天长征化学工程股份有限公司 | Method for producing ethylene glycol from coal |
| CN113856567A (en) * | 2021-11-05 | 2021-12-31 | 华东理工大学 | Ethylene carbonate hydrogenation reactor and application thereof |
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 |
-
2011
- 2011-02-25 CN CN201110046353.1A patent/CN102649698B/en active Active
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 |
|---|
| 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》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111517916A (en) * | 2019-02-02 | 2020-08-11 | 航天长征化学工程股份有限公司 | Method for producing ethylene glycol from coal |
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