CN103804142B - A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol - Google Patents
A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol Download PDFInfo
- Publication number
- CN103804142B CN103804142B CN201210441761.1A CN201210441761A CN103804142B CN 103804142 B CN103804142 B CN 103804142B CN 201210441761 A CN201210441761 A CN 201210441761A CN 103804142 B CN103804142 B CN 103804142B
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- oxalate
- ethylene glycol
- heat exchanger
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of system and method for hydrogenation of oxalate for preparing ethylene glycol. System comprises: circulating hydrogen compressor, input and output material heat exchanger, blender, charging protection bed, recycle hydrogen heater, hydrogenation reactor, feed preheater, product Intermediate Heat Exchanger, reaction discharging cooler and knockout drum, input and output material heat exchanger connects blender, charging protection bed and recycle hydrogen heater successively, and feed preheater connects blender; Recycle hydrogen heater outlet connects hydrogenation reactor import, and hydrogenation reactor outlet connects input and output material heat exchanger, product Intermediate Heat Exchanger, reaction discharging cooler and knockout drum successively. Method comprises: hydrogen and oxalate are mixed to vaporization completely after heating, enters hydrogenation reactor reaction and makes ethylene glycol. The present invention can effectively ensure the reaction condition needing, and stable controls reactor bed temperature rise, fully recovers energy, reduces energy consumption, ensures the selective of the conversion ratio of oxalate and product ethylene glycol.
Description
Technical field
The present invention relates to ethylene glycol and manufacture field, furtherly, relate to a kind of system of hydrogenation of oxalate for preparing ethylene glycolAnd method.
Background technology
Ethylene glycol is important industrial chemicals and strategic materials, mainly for the manufacture of synthetic fibers (terylene), polyester, polyesterPolyalcohol, explosive, glyoxal etc., and as antifreezing agent, plasticizer, hydraulic fluid, surfactant and solvent. Close organicThere is extensive use in the fields such as one-tenth, pharmacy, spices, coating.
The ethylene glycol production method that petrochemical industry is traditional is that gaseous ethene reacts generation oxirane, oxirane with pure oxygenAfter separating from reaction discharging gas, then with water generation hydration reaction generating glycol. In traditional ethylene glycol production method,Oxidation reactor and entry mixers manufacture and design difficulty, the interlocked control safe class of system requires high. Reason is etheneDirectly mix with pure oxygen, must strictly control ethene in explosive range, and will avoid producing static, ethylene simultaneouslyReaction is strong exothermal reaction, and temperature runaway easily occurs. Traditional hydration reaction has not only generated ethylene glycol in addition, also has more diethylGlycol, triethylene glycol and many ethylene glycol produce, ethylene glycol selectively in 90% left and right. After hydration reaction, need through dehydration, second twoThe refining link of alcohol separates and obtains ethylene glycol product, causes that technological process is long, equipment is many, energy consumption is high, thereby also directly has influence on secondThe production cost of glycol. In recent years, under catalyst action, to carry out esterification anti-for external oxirane newly developed and carbon dioxideAnswer, be then hydrolyzed the ethylene carbonate method process route of generating glycol, glycol selectivity can be reached more than 99%,More traditional hydration has a clear superiority in, but this method still relies on oxirane raw material.
20 century 70s, are subject to the impact of world oil crisis, and various countries begin one's study one after another taking coal as raw material production second twoThe method of alcohol. Coal-ethylene glycol is the New Coal Chemical technology taking coal as raw material, and this technology is to obtain CO, hydrogen through coal gasification,Obtain again the process of ethylene glycol through the also further hydrofinishing of carbonylation oxalic ester. Ube Industries Ltd. and U.S. UCC public affairsDepartment has developed jointly by the process route of buty oxalate synthesizing glycol, and this technique will be passed through carbonylation and two mistakes of hydrogenationJourney, first, taking carbon monoxide and butanols as raw material, carries out carbonylation liquid phase reactor, oxalic butyl ester, and then add through liquid phaseH-H reaction, generating glycol. Ube Industries Ltd. develops again the gaseous techniques of carbonylation hydrogenation technique on liquid phase method basis,What can make ethylene glycol selectively reaches 95%, the industry application but external coal-ethylene glycol technology does not all obtain maximizing.
Hydrogenation of oxalate for preparing ethylene glycol is an important directions of Coal Chemical Industry industry, its production method and technological process inThe research and development phase, the current oxalate preparing ethylene glycol industrialized unit that there is no in the world a set of maturation. Hydrogenation of oxalate for preparing ethylene glycolReaction more complicated, under hydrogenation catalyst effect, hydrogenation reaction point multistep is carried out, and ethylene glycol is the intermediate product of reaction.
The main reaction occurring is as follows:
ROOCCOOR+4H2→HOCH2CH2OH+2ROH
The main side reaction occurring is:
HOCH2CH2OH+H2→CH3CH2OH+H2O
Develop the system and method for rational hydrogenation of oxalate for preparing ethylene glycol, its object is just that reaction system can meet insteadShould require, selectively can the ensureing of the conversion ratio of reaction raw materials and ethylene glycol, simultaneity factor arranges appropriately, takes into full account jointEnergy.
The method of the preparing ethylene glycol from oxalic ester that Chinese patent CN101475442A announces is used two or more reactorsSeries connection, first oxalate raw material, first strand of solvent and first strand of hydrogen enter the first reaction zone, contact with catalyst I, and generation containsFirst strand of reaction effluent of ethylene glycol; First strand of reaction effluent and second strand of solvent, second strand of hydrogen are mixed at leastA second reaction zone, I contacts with catalyst I, generates the second strand of reaction effluent that contains ethylene glycol. Said method object isFor ease of the performance of detecting catalyst, in fact in CN101475442A, announcing is more feature, the composition and right of catalystThe requirement of operating condition.
US Patent No. 4112245A has announced a kind of process of vapor phase method Hydrogenation ethylene glycol. The method has comprisedTo the requirement of oxalate raw material composition, reaction temperature, reaction pressure, air speed, catalyst and carrier feature. US4112245A focuses onEmphasize the impact of each factor, do not relate to technological process.
Summary of the invention
For solve problems of the prior art, the invention provides a kind of hydrogenation of oxalate for preparing ethylene glycol system andMethod. Can stablize and control reactor temperature rise, effectively recover energy, reduce energy consumption, ensure conversion ratio and the product second of oxalateGlycol selective.
One of object of the present invention is to provide a kind of system of hydrogenation of oxalate for preparing ethylene glycol.
Comprise:
Circulating hydrogen compressor, input and output material heat exchanger, blender, charging protection bed, recycle hydrogen heater, hydrogenation reactor,Feed preheater, product Intermediate Heat Exchanger, reaction discharging cooler and knockout drum,
Input and output material heat exchanger connects blender, charging protection bed and recycle hydrogen heater successively, and feed preheater connects mixedClose device; Recycle hydrogen heater outlet connects hydrogenation reactor import,
Hydrogenation reactor outlet connects input and output material heat exchanger, product Intermediate Heat Exchanger, reaction discharging cooler successivelyAnd knockout drum;
Knockout drum top exit pipeline connects circulating hydrogen compressor and input and output material heat exchanger successively; At the bottom of knockout drumPortion's pipeline coupled reaction product Intermediate Heat Exchanger, product Intermediate Heat Exchanger top exit is communicated with out-of-bounds;
Pipeline between knockout drum and circulating hydrogen compressor is provided with the pipeline of releasing.
Described blender, charging protection bed and recycle hydrogen heater are preferably arranged near hydrogenation reactor entrance;
Described hydrogenation reactor can adopt fixed bed reactors, shell and tube reactor, moving bed or fluidized-bed reactor etc.,Preferred isothermal shell and tube reactor in the present invention.
Described effluent exchanger, blender, recycle hydrogen heater and hydrogenation reactor can be one, also can many alsoConnection, determines according to actual conditions, preferably two or three parallel connections;
Described charging protection bed can remove remaining pressed powder or particle, can adopt common establishing in this areaStandby, play the effect of removing, preferred fixed bed or filter in the present invention.
Described recycle hydrogen heater be for can adopt common firing equipment in this area, as electrical heating, Steam Heating or addHot stove etc.
Two of object of the present invention is to provide a kind of method of hydrogenation of oxalate for preparing ethylene glycol.
Comprise:
Hydrogen and oxalate are mixed to vaporization completely after heating, enter hydrogenation reactor reaction and make ethylene glycol.
Specifically comprise the following steps:
(a) hydrogen feed and oxalate charging enter respectively blender and are mixed to vaporization completely after heating, enter chargingProtection bed removes remaining pressed powder or particle, is heated to 180～250 DEG C through recycle hydrogen heater, enters hydrogenation reactorReaction, hydrogenation reaction actuator temperature is 150 ~ 300 DEG C, and pressure is 2.0～6.0MPag, and weight space velocity is 0.01 ~ 10h-1；
(b) hydrogenation reactor discharging successively with hydrogen feed and the heat exchange of vapor-liquid separation tank liquid product, after cooling, enterKnockout drum;
(c) the isolated liquid product of knockout drum through with hydrogenation products heat exchange after enter later separation unit, topHydrogen rich gas circulates in system by circulating hydrogen compressor, and maintains non-hydrogen in recycle hydrogen system by the pipeline of releasing and containAmount is stable.
Wherein,
Described hydrogen feed enters blender after being heated to 150 ~ 300 DEG C;
After being heated to 100 ~ 200 DEG C, described oxalate charging enters blender;
Described hydrogenation reactor discharging enters knockout drum after being cooled to 40 ~ 80 DEG C.
Specifically, method of the present invention can comprise hydrogenation reaction part, heat-exchange network part and recycle hydrogen portionPoint.
Hydrogenation reaction part comprises: raw hydrogen is mixed with recycle hydrogen, is heated to after 150 ~ 300 DEG C through input and output material heat exchangerEnter blender. In blender, hydrogen fully mixes with the oxalate raw material after preheating, and oxalate is vaporized completely. Gaseous mixtureBody removes remaining pressed powder or particle through charging protection bed, is then heated to the temperature of 180～250 DEG C through recycle hydrogen heaterDegree enters hydrogenation reactor. Multilayer temperature point is set in hydrogenation reactor, distributes and maximum temperature rise with detected temperatures. HydrogenationIn reactor inlet, outlet and bed, be provided with high temperature interlocking, in the time that temperature reaches setting value, interlocking cut off oxalate charging andThe thermal source of recycle hydrogen heater.
Heat-exchange network part comprises: hydrogenation reactor gas phase drop temperature is 180 ~ 350 DEG C. Reactor discharging and recycle hydrogenHeat exchange, can be preheating to recycle hydrogen 150 ~ 300 DEG C. Reaction discharging again with the heat exchange of vapor-liquid separation tank bottom liquid phases, by liquid productBe preheating to 80 ~ 150 DEG C. Final reaction discharging is through being further cooled to 40 ~ 80 DEG C of laggard knockout drums.
Recycle hydrogen part comprises: reaction discharging is entered knockout drum with the form of gas-liquid two-phase, and liquid product enters follow-up pointFrom unit, gas phase is removed circulating hydrogen compressor, compressor delivery pressure 2.0 ~ 6.0MPaG. On circulating hydrogen compressor suction line, establishPut the pipeline of releasing. In hydrogen feed, contain impurity, in hydrogenation reactor, side reaction produces accessory substance, enters at circulating hydrogen compressorOn mouth pipeline, the pipeline of releasing is set, discharges a small amount of gas by the pipeline of releasing, avoided the long-pending of the interior non-hydrogen of recycle hydrogen systemTired, be beneficial to the stable operation of whole reaction system. Circulating hydrogen compressor can be reciprocating can be also centrifugal, outlet lineUpper flowmeter is established low discharge interlocking, ensures recycle hydrogen flow, takes in time heat in hydrogenation reactor out of.
One of key of the present invention is heated to 150 ~ 300 DEG C of laggard blenders for hydrogen feed heater via, and oxalate is formerMaterial enters and in blender, mixes with hydrogen and vaporize after being heated to 100 ~ 200 DEG C, directly enters hydrogenation reaction with the form of gas phaseDevice. Both ensured the vaporization requirement of reaction feed, shortened as far as possible again the time of staying of oxalate in high-temperature region, and avoided decomposing.By the heating load of control heater, maintain the stable of hydrogenation reactor inlet temperature.
Two of key of the present invention is protected bed for mixer outlet gas directly enters charging. Filling inertia porcelain in protection bedBall, because mixer outlet gas may contain solid particle or powder, easily clog downstream heat exchanger and reactor, therefore arrange protectionBed can, by impurity particle or powder filter, ensure the stable operation of upstream device.
Hydrogenation reactor operating temperature is 180 ~ 300 DEG C, and operating pressure is 2.0～6.0MPag, weight space velocity is 0.01 ~10h-1Lower reaction.
Oxalate hydrogenation is exothermic reaction, is to control the temperature rise of bed, and type of reactor such as can adopt anti-at the hotbedAnswer device, reactor is removed the mode of thermal recovery reactor shell-side generation steam or refrigerant cycle, multilayer temperature is set waiting in hotbedMeasuring point, distributes and controls reaction temperature rising with detected temperatures. When unit scale becomes large, can adopt many isothermal bed bioreactors behaviour in parallelDo; Or the mode that adopts the hotbed parallel connections such as many to connect with adiabatic reactor again, to wait hotbed control reaction temperature rising, ensure with adiabatic reactorThe degree that reactant transforms.
The present invention's the 3rd key point be reactor discharging first with recycle hydrogen heat exchange, and then with vapor-liquid separation pot bottomLiquid phase material heat exchange, finally cooling by public work, oxalate raw material mixes with the circulating hydrogen after preheating. This changesHeated succession, had both effectively reclaimed energy, avoided again oxalate and excessive temperature media for heat exchange and aggravate decompose, be conducive to improveThe yield of reaction.
System and method tool of the present invention has the following advantages:
The type of reactor that adopts isothermal reactor or isothermal reactor to connect with adiabatic reactor, both stable controlReactor bed temperature rise, has ensured again abundant conversion.
Hydrogenation reactor entrance arranges blender, liquid phase oxalate by after mixing with recycle hydrogen gas completely vaporization, withThe form of gas phase is directly entered hydrogenation reactor, has both met gas-phase feed requirement, at utmost shortens again raw material stopping in high-temperature regionStay the time, reduced the decomposition of oxalate.
Mixer outlet arranges protection bed, and entrained solid particle and powder in filtering gas, ensured downstream in timeThe stable operation of equipment.
By heat exchange order is rationally set, recover energy to the full extent, reduce system energy consumption. Also avoided grass simultaneouslyAcid esters and high-temperature medium heat exchange, reduce the possibility of decomposing, and improved reaction yield, the conversion ratio of guarantee oxalate and ethylene glycolSelectively.
Brief description of the drawings
The reaction system schematic diagram of Fig. 1 embodiment 1 of the present invention
The reaction system schematic diagram of Fig. 2 embodiment 2 of the present invention
Description of reference numerals:
1-circulating hydrogen compressor 2-input and output material heat exchanger 3-blender
4-charging protection bed 5-recycle hydrogen heater 6-hydrogenation reactor
7-feed preheater 8-product Intermediate Heat Exchanger 9-reaction discharging cooler
The charging of 10-knockout drum 11-hydrogen feed 12-oxalate
The 13-liquid phase target product 14-cold medium 16-of the pipeline 15-thermal medium of releasing
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
As shown in Figure 1, a kind of system of hydrogenation of oxalate for preparing ethylene glycol, comprising: circulating hydrogen compressor 1, input and output material heat exchangeIn the middle of device 2, blender 3, charging protection bed 4, recycle hydrogen heater 5, hydrogenation reactor 6, feed preheater 7, product, changeHot device 8, reaction discharging cooler 9 and knockout drum 10;
Input and output material heat exchanger 2 connects blender 3, charging protection bed 4 and recycle hydrogen heater 5 successively, and feed preheater 7 connectsConnect blender 3; 5 outlets of recycle hydrogen heater connect hydrogenation reactor 6 imports, and hydrogen feed 11 is through input and output material heat exchanger 2, mixingDevice 3, charging protection bed 4 and recycle hydrogen heater 5 enter hydrogenation reactor 6; Oxalate charging 12 is through feed preheater 7 and mixingDevice 3 enters charging protection bed 4;
Hydrogenation reactor 6 export connect successively input and output material heat exchanger 2, product Intermediate Heat Exchanger 8, reaction discharging is coolingDevice 9 and knockout drum 10;
Knockout drum 10 top exit pipelines connect circulating hydrogen compressor 1 and input and output material heat exchanger 2 successively; Gas-liquid separationBottom line coupled reaction product Intermediate Heat Exchanger 8 is rear drains into downstream separation system as liquid product 13 for tank 8;
Pipeline between knockout drum 10 and circulating hydrogen compressor 1 is provided with the pipeline 14 of releasing.
Hydrogenation reactor 5 is single bed shell-and-tube reactor.
Charging protection bed is fixed bed.
Raw hydrogen 11 is mixed with recycle hydrogen, enters mixing after being warming up to 200 DEG C after input and output material heat exchanger 2 reclaims heatDevice 3. Raw material oxalate 12 is preheated to 140 DEG C of laggard blenders 3 through feed preheater 7. In blender 3, hydrogen and oxalateFully mix, and oxalate is vaporized completely.
Blender 3 dischargings enter charging protection bed 4 and remove remaining pressed powder or particle, then through recycle hydrogen heater5, for ensureing hydrogenation effect, recycle hydrogen heater outlet temperature is 200～230 DEG C, and after heating, reaction mass enters hydrogenation reactionDevice 6. For ensureing hydrogenation effect, hydrogenation reactor 6 operating temperatures are at 200 ~ 250 DEG C, and operating pressure is at 2.8 ~ 3.5MPaG. WeightAir speed is 0.1 ~ 1.0h-1. In hydrogenation reactor 6, oxalate and hydrogen reaction generating glycol. Hydrogenation reaction is that heat release is anti-Should, a reaction heat part is removed thermal medium and is taken away, byproduct steam, and another part heat goes out hydrogenation reactor 6 with reflecting material strip.
Reaction discharging is reclaimed heat through heat-exchange network. First by input and output material heat exchanger 2 and recycle hydrogen heat exchange, then enterProduct Intermediate Heat Exchanger 8 and vapor-liquid separation tank 10 bottom liquid phases material-heat-exchangings, the most laggard material cooler 9 that reflects, by coldAfter but to 40 DEG C, enter knockout drum 10 with the form of two phase flow.
The isolated liquid phase target product 13 of knockout drum 10 changes with product in product Intermediate Heat Exchanger 8After heat, enter downstream separation system. Density of hydrogen 95mol% left and right from the gas phase out of knockout drum 10 tops, as followingRing hydrogen send circulating hydrogen compressor 1, the laggard circulatory system of boosting.
Adopt oxalate hydrogenation catalyst, catalyst weight air speed is 0.1 ~ 0.5h-1, 10 DEG C of bed maximum temperature rises.
Adopt flow process as shown in Figure 1, obtain the result of table 1.
Result shows, adopts system and method preparing ethylene glycol of the present invention, and isothermal reactor bed maximum temperature rise can be controlledIn 10 DEG C, the conversion ratio of oxalate is greater than 98%, and glycol selectivity is greater than 90mol%, by removing heat and heat-exchange networkRecover energy, yield is 1.985Mkcal/t ethylene glycol.
Table 1
Embodiment 2
System is identical with embodiment 1, and difference is only input and output material heat exchanger 2, blender 3, recycle hydrogen heater 5, hydrogenationReactor 6 is two parallel connections: as shown in Figure 2.
Adopt oxalate hydrogenation catalyst, catalyst weight air speed is 0.1 ~ 0.5h-1, bed maximum temperature rise is less than 10 DEG C.
Adopt flow process as shown in Figure 2, obtain the result of table 2.
Result shows, adopts system and method preparing ethylene glycol of the present invention, and isothermal reactor bed maximum temperature rise can be controlledIn 10 DEG C, the conversion ratio of oxalate is greater than 98%, and glycol selectivity is greater than 90mol%, by removing heat and heat-exchange networkRecover energy, yield is 1.985Mkcal/t ethylene glycol.
Table 2
Claims (9)
1. a device for hydrogenation of oxalate for preparing ethylene glycol, is characterized in that described device comprises:
Circulating hydrogen compressor, input and output material heat exchanger, blender, charging protection bed, recycle hydrogen heater, hydrogenation reactor, raw materialPreheater, product Intermediate Heat Exchanger, reaction discharging cooler and knockout drum;
Input and output material heat exchanger connects blender, charging protection bed and recycle hydrogen heater successively, and feed preheater connects blender;Recycle hydrogen heater outlet connects hydrogenation reactor import;
It is gentle that hydrogenation reactor outlet connects input and output material heat exchanger, product Intermediate Heat Exchanger, reaction discharging cooler successivelyLiquid knockout drum;
Knockout drum top exit pipeline connects circulating hydrogen compressor and input and output material heat exchanger successively; Knockout drum lower tubeLine coupled reaction product Intermediate Heat Exchanger, product Intermediate Heat Exchanger top exit is communicated with out-of-bounds;
Pipeline between knockout drum and circulating hydrogen compressor is provided with the pipeline of releasing.
2. the device of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, is characterized in that:
Described blender, charging protection bed and recycle hydrogen heater are arranged near hydrogenation reactor entrance.
3. the device of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, is characterized in that:
Described hydrogenation reactor is isothermal shell and tube reactor.
4. the device of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, is characterized in that:
Described input and output material heat exchanger, blender, recycle hydrogen heater and hydrogenation reactor are many parallel connections.
5. the device of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, is characterized in that:
Described charging protection bed is fixed bed or filter.
6. the device of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, is characterized in that:
Described recycle hydrogen heater is electrical heating, Steam Heating or heating furnace.
7. a method for the hydrogenation of oxalate for preparing ethylene glycol device of employing as described in one of claim 1～6, is characterized in thatDescribed method comprises:
Hydrogen and oxalate are mixed to vaporization completely after heating, enter hydrogenation reactor reaction and make ethylene glycol.
8. the method for hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 7, is characterized in that described method comprises:
(a) hydrogen feed and oxalate charging enter respectively blender and are mixed to vaporization completely after heating, enter charging protectionBed removes remaining pressed powder or particle, is heated to 180～250 DEG C through recycle hydrogen heater, enters hydrogenation reactor reaction,Hydrogenation reaction actuator temperature is 150～300 DEG C, and pressure is 2.0～6.0MPag, and weight space velocity is 0.01～10h-1；
(b) hydrogenation reactor discharging successively with hydrogen feed and the heat exchange of vapor-liquid separation tank liquid product, after cooling, enter gas-liquidKnockout drum;
(c) the isolated liquid product of knockout drum through with hydrogenation products heat exchange after enter later separation unit, the rich hydrogen in topGas phase circulates in system by circulating hydrogen compressor, and it is steady to maintain in recycle hydrogen system non-hydrogen content by the pipeline of releasingFixed.
9. the method for hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 8, is characterized in that:
Described hydrogen feed enters blender after being heated to 150～300 DEG C;
After being heated to 100～200 DEG C, described oxalate charging enters blender;
Described hydrogenation reactor discharging enters knockout drum after being cooled to 40～80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210441761.1A CN103804142B (en) | 2012-11-07 | 2012-11-07 | A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210441761.1A CN103804142B (en) | 2012-11-07 | 2012-11-07 | A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103804142A CN103804142A (en) | 2014-05-21 |
| CN103804142B true CN103804142B (en) | 2016-05-11 |
Family
ID=50701585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210441761.1A Active CN103804142B (en) | 2012-11-07 | 2012-11-07 | A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804142B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439816B (en) * | 2014-08-27 | 2017-10-27 | 中国石油化工股份有限公司 | Acetic acid ester through hydrogenation produces the process of ethanol |
| CN105418366B (en) * | 2015-12-27 | 2018-03-09 | 安徽淮化股份有限公司 | A kind of safety interlock and its application method for coal-ethylene glycol technique |
| CN105566171B (en) * | 2016-02-29 | 2017-06-16 | 江苏吉华化工有限公司 | A kind of device for preparing H acid |
| CN108947769A (en) * | 2018-08-15 | 2018-12-07 | 鄂尔多斯市新杭能源有限公司 | Ethylene glycol preparation facilities |
| CN112759505B (en) * | 2019-10-21 | 2024-01-30 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| CN111018671B (en) * | 2020-01-03 | 2024-04-16 | 东华工程科技股份有限公司 | System for synthesizing ethylene glycol through dimethyl oxalate hydrogenation and preparation method thereof |
| CN113563158B (en) * | 2020-04-28 | 2023-09-29 | 惠生工程（中国）有限公司 | Process for producing ethylene glycol and co-producing methanol from ethylene carbonate |
| CN111732497A (en) * | 2020-07-21 | 2020-10-02 | 濮阳永金化工有限公司 | Device for improving hydrogen-ester ratio and application method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751334A (en) * | 1985-06-04 | 1988-06-14 | Davy Mckee (London) Limited | Process for the production of butane-1,4-diol |
| US6683224B1 (en) * | 1995-05-03 | 2004-01-27 | Cognis Deutschland Gmbh & Co. Kg | Process for the production of fatty alcohols |
| CN102060664A (en) * | 2010-12-23 | 2011-05-18 | 西南化工研究设计院 | High-efficiency and energy-saving reaction process for preparing ethylene glycol through hydrogenation of oxalate |
| CN202139179U (en) * | 2011-01-17 | 2012-02-08 | 山东华鲁恒升集团德化设计研究有限公司 | Device for producing ethylene glycol by dimethyloxalate with hydrogenation |
| CN202450010U (en) * | 2011-12-28 | 2012-09-26 | 安徽淮化股份有限公司 | Hydrogenation reaction device system for use in ethylene glycol industrial production |
-
2012
- 2012-11-07 CN CN201210441761.1A patent/CN103804142B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751334A (en) * | 1985-06-04 | 1988-06-14 | Davy Mckee (London) Limited | Process for the production of butane-1,4-diol |
| US6683224B1 (en) * | 1995-05-03 | 2004-01-27 | Cognis Deutschland Gmbh & Co. Kg | Process for the production of fatty alcohols |
| CN102060664A (en) * | 2010-12-23 | 2011-05-18 | 西南化工研究设计院 | High-efficiency and energy-saving reaction process for preparing ethylene glycol through hydrogenation of oxalate |
| CN202139179U (en) * | 2011-01-17 | 2012-02-08 | 山东华鲁恒升集团德化设计研究有限公司 | Device for producing ethylene glycol by dimethyloxalate with hydrogenation |
| CN202450010U (en) * | 2011-12-28 | 2012-09-26 | 安徽淮化股份有限公司 | Hydrogenation reaction device system for use in ethylene glycol industrial production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804142A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103804142B (en) | A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol | |
| CN102775274B (en) | System and method for preparing ethylene glycol through oxalate hydrogenation | |
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN102942446B (en) | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation | |
| CN103467248B (en) | A kind of energy-saving ester through hydrogenation technique | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN104557371B (en) | A kind of fixed bed adiabatic reactor single stage method methanol conversion produces the method for hydrocarbon mixture | |
| CN103709001B (en) | The method of Synthesis of Ethylene Glycol by Ethylene Oxide Hydration | |
| CN106748631A (en) | A kind of monochloro methane energy-saving processing technique and device | |
| CN101531337B (en) | Method and device for low-pressure processing of coal coking gas | |
| CN205295183U (en) | Energy -saving ultra -large methanol synthesis device of production different brackets steam | |
| CN105418365A (en) | Novel synthetic-gas-to-ethylene-glycol hydrogenation unit | |
| CN106608865A (en) | Energy-saving method for synthesizing ethylene carbonate | |
| Goosheneshin et al. | Simultaneous production and utilization of methanol for methyl formate synthesis in a looped heat exchanger reactor configuration | |
| CN203782064U (en) | Reactor for synthesizing propylene carbonate or ethylene carbonate by utilizing urea and propylene glycol or ethylene glycol | |
| CN102050710B (en) | Method for preparing 2-methylacraldehyde and 2-methyl-2-pentenal synchronously | |
| CN108586213A (en) | A kind of waste-heat recovery device in ethene hydroformylation reaction process and its method | |
| CN103708999B (en) | Catalysis hydration is produced the method for ethylene glycol | |
| CN111116335B (en) | Process for preparing acrolein or methacrolein | |
| CN208545336U (en) | A kind of waste-heat recovery device in ethene hydroformylation reaction process | |
| CN105924329A (en) | Coupling production process for preparing alcohol through acetic acid | |
| CN209193849U (en) | A kind of nitrobenzene continuously hydrogen adding Aniline Unit | |
| CN105237318A (en) | Transcritical CO2 catalytic esterification/condensation-separation coupling reaction method and equipment | |
| CN202671463U (en) | Device for preparing oxalate by CO gas-phase coupling | |
| CN207102568U (en) | A kind of aromatisation plant modification into isomerization unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: China Petrochemical Group Co., Ltd Patentee after: Sinopec Engineering Construction Co., Ltd Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: China Petrochemical Corp Patentee before: Sinopec Engineering Construction Co., Ltd |
|
| CP01 | Change in the name or title of a patent holder |