CN102775274A - System and method for preparing ethylene glycol through oxalate hydrogenation - Google Patents
System and method for preparing ethylene glycol through oxalate hydrogenation Download PDFInfo
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- CN102775274A CN102775274A CN2011101238723A CN201110123872A CN102775274A CN 102775274 A CN102775274 A CN 102775274A CN 2011101238723 A CN2011101238723 A CN 2011101238723A CN 201110123872 A CN201110123872 A CN 201110123872A CN 102775274 A CN102775274 A CN 102775274A
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Abstract
The invention discloses a system and a method for preparing ethylene glycol through oxalate hydrogenation. The system includes: a circulating hydrogen compressor, a charge and discharge heat exchanger, a heater, a mixer, a hydrogenation reactor, a raw material preheater, a reaction discharge cooler, and a gas-liquid separation tank. The method consists of: (a) heating a hydrogen charge material and an oxalate charge material respectively and then bringing them into the mixer, mixing them for complete gasification, and letting the gas enter the hydrogenation reactor directly; (b) subjecting a discharge material of the hydrogenation reactor to heat exchange with the hydrogen charge material and the oxalate charge material, cooling the discharge material and bringing it into the gas-liquid separation tank; and (c) making a liquid phase target product separated by the gas-liquid separation tank enter a subsequent separation unit, letting a hydrogen-rich gas phase enter systemic circulation, and maintaining a stable non-hydrogen gas content in the circulating hydrogen system through a discharge pipeline. Employment of the system and method disclosed in the inventive can effectively guarantee the needed reaction conditions, stably control the temperature rise of a reactor bed, full recover energy, reduce energy consumption, and ensure the conversion rate of oxalate and the selectivity of the ethylene glycol product.
Description
Technical field
The present invention relates to chemical field, say further, relate to a kind of system and method for hydrogenation of oxalate for preparing ethylene glycol.
Background technology
The terepthaloyl moietie working method that petrochemical industry is traditional is that gaseous ethene and pure oxygen reaction generate oxyethane, and oxyethane generates terepthaloyl moietie with water generation hydration reaction after from reaction discharging gas, separating again.In traditional terepthaloyl moietie working method, oxidation reactor and entry mixers manufacture and design difficulty, the interlocked control safe class of system requires high.Reason is that ethene directly mixes with pure oxygen, must strictly control ethene in XPL range, and will avoid producing static, and ethylene oxidation reactions is a strong exothermal reaction simultaneously, and temperature runaway takes place easily.Traditional in addition hydration reaction has not only generated terepthaloyl moietie, also has more Diethylene Glycol, triethylene glycol and many terepthaloyl moietie to produce, and the selectivity of terepthaloyl moietie is about 90%.Need to separate obtaining the terepthaloyl moietie product after the hydration reaction, cause that technical process is long, equipment is many, energy consumption is high, thereby also directly have influence on the production cost of terepthaloyl moietie through dehydration, the refining link of terepthaloyl moietie.In recent years; External oxyethane newly developed and carbonic acid gas carry out esterification under catalyst action; Hydrolysis generates the NSC 11801 method operational path of terepthaloyl moietie then; Make glycol selectivity can reach more than 99%, more traditional hydration has a clear superiority in, but this method still relies on the oxyethane raw material.
Hydrogenation of oxalate for preparing ethylene glycol is an important directions of Coal Chemical Industry industry, and its working method and technical process are in the research and development phase, and still none overlaps sophisticated barkite preparing ethylene glycol industrialized unit in the world at present.The reaction more complicated of hydrogenation of oxalate for preparing ethylene glycol, under the hydrogenation catalyst effect, hydrogenation reaction branch multistep is carried out, and terepthaloyl moietie is the intermediate product of reaction.
The main reaction that takes place is following:
ROOCCOOR +?4H
2 →?HOCH
2CH
2OH?+?2ROH
The main side reaction that takes place is:
HOCH
2CH
2OH + H
2 →?CH
3CH
2OH + H
2O
Develop the system and method for rational hydrogenation of oxalate for preparing ethylene glycol, its purpose just is that reactive system can satisfy the reaction requirement, and the transformation efficiency of reaction raw materials and the selectivity of terepthaloyl moietie can guarantee that simultaneity factor is provided with appropriately, take into full account energy-conservation.
The method of the preparing ethylene glycol from oxalic ester that Chinese patent CN101475442A announces is used two or more reactors in series; Barkite raw material, first strand of solvent and first strand of hydrogen at first advance first reaction zone; Contact with catalyst I, generate the first strand of reaction effluent that contains terepthaloyl moietie; First strand of reaction effluent and second strand of solvent, second strand of hydrogen are mixed at least one second reaction zone, and I contacts with catalyst I, generate the second strand of reaction effluent that contains terepthaloyl moietie.The aforesaid method purpose is the performance for ease of detecting catalyst, in fact announce among the CN101475442A more be catalyzer characteristic, form and to the requirement of operational condition.
U.S. Pat 4112245A has announced a kind of process method of vapor phase process hydrogenation preparing ethylene glycol.This method has comprised the requirement to barkite raw material composition, temperature of reaction, reaction pressure, air speed, catalyzer and carrier characteristic.US4112245A focuses on the influence of each factor of stressing, does not relate to technical process.
Summary of the invention
For solving the problem that exists in the prior art, the invention provides a kind of system and method for hydrogenation of oxalate for preparing ethylene glycol.Can stablize the controlling reactor temperature rise, the efficient recovery energy, cut down the consumption of energy, guarantee the transformation efficiency of barkite and the selectivity of product terepthaloyl moietie.
One of the object of the invention provides a kind of system of hydrogenation of oxalate for preparing ethylene glycol.
Comprise: circulating hydrogen compressor 1, input and output material interchanger 2, well heater 3, mixing tank 4, hydrogenator 5, feed preheater 6, reaction discharging water cooler 7 and knockout drum 8.
Input and output material interchanger 2 connects well heater 3 and mixing tank 4 successively, and feed preheater 6 connects mixing tank 4; Mixing tank 4 outlets connect hydrogenator 5 imports, and hydrogen feed 9 gets into hydrogenator 5 through input and output material interchanger 2, well heater 3 and mixing tank 4; Barkite charging 10 gets into hydrogenator 5 through feed preheater 6 and mixing tank 4.
Knockout drum 8 top exit pipelines connect circulating hydrogen compressor 1 and input and output material interchanger 2 successively; Knockout drum 8 outlet at bottoms are discharged liquid phase title product 11 to system.
Pipeline between knockout drum 8 and the circulating hydrogen compressor 1 is provided with the pipeline 12 of releasing.
Said mixing tank 4 as close as possible hydrogenator 5 inlets.
Said hydrogenator 5 is the combination of isothermal shell and tube reactor or isothermal shell-and-tube reactor and fixed bed adiabatic reactor.
Said well heater 3 is electrically heated, steam heating or process furnace.
Two of the object of the invention provides a kind of method of hydrogenation of oxalate for preparing ethylene glycol.
Comprise following steps:
(a) hydrogen feed and barkite charging get into mixer mixing respectively through heating back, and barkite mixes with hydrogen and is gasified totally, and directly get into hydrogenator with the form of gas phase and react.The hydrogenation reaction actuator temperature is 180 ~ 300 ℃, and pressure is 2.0～6.0MPag, and weight space velocity is 0.01 ~ 10 h
-1
(b) the hydrogenator discharging successively with hydrogen feed and barkite charging heat exchange, through cooling back entering knockout drum;
(c) the isolated liquid phase title product of knockout drum gets into the later separation unit, and gas phase gets into circulating hydrogen compressor, and it is stable to keep in the recycle hydrogen system non-hydrogen gas content through the pipeline of releasing.
Specifically, method of the present invention can comprise hydrogenation reaction part, heat exchanger network part and recycle hydrogen part.
Hydrogenation reaction partly comprises: raw hydrogen 9 is mixed with recycle hydrogen, and through 2 preheatings of input and output material interchanger, heater via 3 is heated to 150 ~ 350 ℃ of laggard mixing tanks 4 again.Barkite raw material 10 thorough mixing in mixing tank 4 after hydrogen and the preheating, and barkite vaporized fully.Mixed gas gets into hydrogenator 5 with 150 ~ 300 ℃ temperature.The multilayer temperature point is set in hydrogenator, distributes and maximum temperature rise with detected temperatures.Be provided with the high temperature interlocking in hydrogenator 5 inlets, outlet and the bed, when temperature reached set(ting)value, interlocking cut off the thermal source of barkite charging 10 and well heater 3.
Heat exchanger network partly comprises: hydrogenator 5 gas phase drop temperatures are 180 ~ 350 ℃.Reactor drum discharging and recycle hydrogen heat exchange can be preheating to 110 ~ 250 ℃ with recycle hydrogen.The reaction discharging again with 10 heat exchange of barkite raw material, barkite is preheating to 110 ~ 200 ℃.The final reaction discharging is through further being cooled to 40 ~ 100 ℃ of laggard knockout drums 8.
Recycle hydrogen partly comprises: the reaction discharging is with the form air inlet liquid separating tank 8 of gas-liquid two-phase, and liquid phase title product 11 enters the later separation unit, and gas phase is removed circulating hydrogen compressor 1, compressor delivery pressure 2.0 ~ 6.0MPaG.The pipeline 12 of releasing is set on circulating hydrogen compressor 1 source line.Knockout drum is provided with high level chain, when liquid level reaches the interlocking liquid level, stops circulating hydrogen compressor, guarantees the safety operation of unit.Contain impurity in the hydrogen feed 9; Side reaction produces in the hydrogenator 5 has by product, and the pipeline of releasing is set on the circulating hydrogen compressor source line, and pipeline is discharged little of gas through releasing; Avoid the accumulation of non-hydrogen in the recycle hydrogen system, be beneficial to the stable operation of entire reaction system.Circulating hydrogen compressor can be reciprocating type also can be centrifugal, under meter is established low flow interlocking on the outlet line, guarantees the recycle hydrogen flow, in time takes heat in the hydrogenator out of.
Wherein:
Said hydrogen feed gets into mixing tank after being heated to 150 ~ 350 ℃.
After being heated to 110 ~ 200 ℃, said barkite charging gets into mixing tank.
Said hydrogenator discharging gets into knockout drum after being cooled to 40 ~ 100 ℃.
Key of the present invention is heated to 150 ~ 350 ℃ of laggard mixing tanks for the hydrogen feed heater via, and the barkite raw material mixes with hydrogen in mixing tank and vaporizes, and directly advances hydrogenator with the form of gas phase.Both guaranteed the vaporization requirement of reaction feed, shortened the residence time of barkite again as far as possible, and avoided decomposing in the high-temperature zone.Through the heating load of control heater, keep the stable of hydrogenator temperature in.
The well heater form can be electrically heated, steam heating, also can be process furnace.
The hydrogenator service temperature is 180 ~ 300 ℃, and working pressure is 2.0～6.0MPag, and weight space velocity is 0.01 ~ 10 h
-1Following reaction.
Oxalate hydrogenation is thermopositive reaction; Be the temperature rise of control bed, the reactor drum pattern can adopt the isothermal bed bioreactor, and reactor drum is removed the mode of thermal recovery reactor drum shell-side generation steam or refrigerant cycle; The multilayer temperature point is set in waiting hotbed, distributes and the control reaction temperature rising with detected temperatures.When unit scale becomes big, can adopt the parallel operation of many isothermal bed bioreactors; Or adopt hotbed parallel connections such as many again with the placed in-line mode of adiabatic reactor, to wait hotbed control reaction temperature rising, guarantee the degree that reactant transforms with adiabatic reactor.
Another key point of the present invention be the reactor drum discharging at first with the recycle hydrogen heat exchange, and then with barkite charging heat exchange, at last through general facilities cooling.This heat exchange order had both effectively reclaimed energy, had avoided barkite and the heat exchange of excessive temperature medium again and aggravated decomposition, helped improving the yield of reaction.
System and method of the present invention has following advantage:
Adopt isothermal reactor or isothermal reactor and the placed in-line reactor drum pattern of adiabatic reactor, both stablized and controlled the reactor bed temperature rise, guaranteed abundant conversion again.
The hydrogenator inlet is provided with mixing tank; The liquid phase barkite through with vaporization fully after recycle hydrogen gas mixes, directly advance hydrogenator with the form of gas phase, both satisfied the gas-phase feed requirement; At utmost shorten the residence time of raw material again, reduced the decomposition of barkite in the high-temperature zone.
Through the heat exchange order rationally is set, recovered energy reduces system energy consumption to the full extent.Also avoid simultaneously barkite and high-temperature medium heat exchange, reduced the possibility of decomposing, improved reaction yield, guaranteed the transformation efficiency of barkite and the selectivity of terepthaloyl moietie.
Description of drawings
The reactive system synoptic diagram of Fig. 1 embodiment 1 according to the invention
The reactive system synoptic diagram of Fig. 2 embodiment 2 according to the invention
Description of reference numerals:
1---circulating hydrogen compressor 2---input and output material interchanger 3---well heater
4---mixing tank 5---hydrogenator 6---feed preheaters
7---reaction discharging water cooler 8---knockout drum 9---hydrogen feed
10---barkite charging 11---the liquid phase title product 12---pipelines of releasing
13---cold medium.
Embodiment
Below in conjunction with embodiment, further specify the present invention, but the present invention does not receive the restriction of embodiment.
Embodiment 1
A kind of system of hydrogenation of oxalate for preparing ethylene glycol comprises: circulating hydrogen compressor 1, input and output material interchanger 2, well heater 3, mixing tank 4, hydrogenator 5, feed preheater 6, reaction discharging water cooler 7 and knockout drum 8.
Input and output material interchanger 2 connects well heater 3 and mixing tank 4 successively, and feed preheater 6 connects mixing tank 4; Mixing tank 4 outlets connect hydrogenator 5 imports, and hydrogen feed 9 gets into hydrogenator 5 through input and output material interchanger 2, well heater 3 and mixing tank 4; Barkite charging 10 gets into hydrogenator 5 through feed preheater 6 and mixing tank 4.
Knockout drum 8 top exit pipelines connect circulating hydrogen compressor 1 and input and output material interchanger 2 successively; Knockout drum 8 outlet at bottoms are discharged liquid phase title product 11 to system.
Pipeline between knockout drum 8 and the circulating hydrogen compressor 1 is provided with the pipeline 12 of releasing.
The reaction discharging is reclaimed heat through heat exchanger network.At first, advance feed preheater 6 heating raw barkites 10 afterwards through input and output material interchanger 2 and recycle hydrogen heat exchange.The reaction discharging advances to react discharging water cooler 7 behind feed preheater 6, be cooled to after 40 ℃ the form air inlet liquid separating tank 8 with two.
Adopt the barkite hydrogenation catalyst, the catalyst weight air speed is 0.1 ~ 0.5 h
-1, 10 ℃ of bed maximum temperature rises.
Adopt flow process as shown in Figure 1, obtain the result of table 1.
The result shows; Adopt system and method preparing ethylene glycol of the present invention; Isothermal reactor bed maximum temperature rise can be controlled in 10 ℃, and the transformation efficiency of barkite is greater than 98%, and glycol selectivity is greater than 90 mol%; Through removing heat and heat exchanger network recovered energy, yield is a 1.47Mkcal/t terepthaloyl moietie.
System is identical with embodiment 1, and difference only is:
Well heater 3 is steam heaters
Adopt the barkite hydrogenation catalyst, the catalyst weight air speed is 0.1 ~ 0.5 h
-1, the bed maximum temperature rise is less than 10 ℃.
Adopt flow process as shown in Figure 2, obtain the result of table 2.
The result shows, adopts system and method preparing ethylene glycol of the present invention, and isothermal reactor bed maximum temperature rise still can be controlled in 10 ℃, waits hotbed barkite transformation efficiency greater than 85%.Unreacted barkite continues reaction at adiabatic reactor, and the bed temperature rise is less than 5 ℃.The overall conversion of barkite is greater than 98%, and the terepthaloyl moietie global selectivity is greater than 90 mol%, through removing heat and heat exchanger network recovered energy, yield 1.45Mkcal/t terepthaloyl moietie.
Claims (8)
1. the system of a hydrogenation of oxalate for preparing ethylene glycol; Comprise: circulating hydrogen compressor (1), input and output material interchanger (2), well heater (3), mixing tank (4), hydrogenator (5), feed preheater (6), reaction discharging water cooler (7) and knockout drum (8) is characterized in that:
Input and output material interchanger (2) connects well heater (3) and mixing tank (4) successively, and feed preheater (6) connects mixing tank (4); Mixing tank (4) outlet connects hydrogenator (5) import, and hydrogen feed (9) gets into hydrogenator (5) through input and output material interchanger (2), well heater (3) and mixing tank (4); Barkite charging (10) gets into hydrogenator (5) through feed preheater (6) and mixing tank (4);
Hydrogenator (5) outlet connects input and output material interchanger (2), feed preheater (6), reaction discharging water cooler (7) and knockout drum (8) successively;
Knockout drum (8) top exit pipeline connects circulating hydrogen compressor (1) and input and output material interchanger (2) successively; Knockout drum (8) outlet at bottom is discharged liquid phase title product (11) to system;
Pipeline between knockout drum (8) and the circulating hydrogen compressor (1) is provided with the pipeline of releasing (12).
2. the system of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, it is characterized in that: mixing tank (4) enters the mouth near hydrogenator (5).
3. the system of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, it is characterized in that: said hydrogenator (5) is an isothermal reactor, or isothermal reactor is connected with adiabatic reactor.
4. the system of hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 1, it is characterized in that: said well heater (3) is electrically heated, steam heating or process furnace.
5. the method for the described hydrogenation of oxalate for preparing ethylene glycol of one of an employing such as claim 1～4 system is characterized in that comprising following steps:
(a) hydrogen feed and barkite charging get into mixer mixing respectively after heating; Barkite and vaporization fully after hydrogen mixes; And directly get into the hydrogenator reaction with the form of gas phase; The hydrogenation reaction actuator temperature is 180 ~ 300 ℃, and pressure is 2.0～6.0MPag, and weight space velocity is 0.01 ~ 10 h
-1
(b) the hydrogenator discharging successively with hydrogen feed and barkite charging heat exchange, through cooling back entering knockout drum;
(c) the isolated liquid phase title product of knockout drum gets into the later separation unit, hydrogen rich gas mutually through circulating hydrogen compressor at system's internal recycle, and it is stable to keep in the recycle hydrogen system non-hydrogen gas content through the pipeline of releasing.
6. the method for hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 5 is characterized in that: through the placed in-line form of isothermal reactor or isothermal reactor and adiabatic reactor being set with the control reaction temperature rising, and guarantee transformation efficiency.
7. the method for hydrogenation of oxalate for preparing ethylene glycol as claimed in claim 5 is characterized in that: hydrogenator (5) inlet is provided with mixing tank (4), the liquid phase barkite with vaporize fully after recycle hydrogen gas mixes, directly advance hydrogenator with gas phase.
8. method as claimed in claim 5 is characterized in that:
Said hydrogen feed gets into mixing tank after being heated to 150 ~ 350 ℃;
After being heated to 110 ~ 200 ℃, said barkite charging gets into mixing tank;
Said hydrogenator discharging gets into knockout drum after being cooled to 40 ~ 100 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015027897A1 (en) * | 2013-09-02 | 2015-03-05 | 东华工程科技股份有限公司 | Energy-saving ester hydrogenation process |
| CN104478658A (en) * | 2014-11-26 | 2015-04-01 | 西南化工研究设计院有限公司 | Technique and device for lowering hydrogen gas circulating rate in hydrogenation reaction process |
| CN104725191A (en) * | 2015-03-24 | 2015-06-24 | 中国五环工程有限公司 | Ethylene glycol refining and separating method and system |
| CN107082741A (en) * | 2017-06-16 | 2017-08-22 | 四川天科技股份有限公司 | A kind of method of oxalate deep hydrogenation catalytic reaction synthesizing glycol |
| CN109207220A (en) * | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of methanation process of coal based synthetic gas preparation synthetic natural gas |
| CN111018671A (en) * | 2020-01-03 | 2020-04-17 | 东华工程科技股份有限公司 | System for synthesizing ethylene glycol by dimethyl oxalate hydrogenation and preparation method thereof |
| 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 |
| CN112759505A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| CN115646377A (en) * | 2022-11-16 | 2023-01-31 | 陕西延长石油（集团）有限责任公司 | Reaction system and method for continuously producing alpha-alkyl ester |
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Cited By (14)
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|---|---|---|---|---|
| WO2015027897A1 (en) * | 2013-09-02 | 2015-03-05 | 东华工程科技股份有限公司 | Energy-saving ester hydrogenation process |
| CN104478658A (en) * | 2014-11-26 | 2015-04-01 | 西南化工研究设计院有限公司 | Technique and device for lowering hydrogen gas circulating rate in hydrogenation reaction process |
| CN104478658B (en) * | 2014-11-26 | 2017-05-03 | 西南化工研究设计院有限公司 | Technique and device for lowering hydrogen gas circulating rate in hydrogenation reaction process |
| CN104725191A (en) * | 2015-03-24 | 2015-06-24 | 中国五环工程有限公司 | Ethylene glycol refining and separating method and system |
| CN107082741B (en) * | 2017-06-16 | 2021-01-26 | 西南化工研究设计院有限公司 | Method for synthesizing ethylene glycol through oxalate deep hydrogenation catalytic reaction |
| CN107082741A (en) * | 2017-06-16 | 2017-08-22 | 四川天科技股份有限公司 | A kind of method of oxalate deep hydrogenation catalytic reaction synthesizing glycol |
| CN109207220A (en) * | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of methanation process of coal based synthetic gas preparation synthetic natural gas |
| CN109207220B (en) * | 2017-06-29 | 2020-10-30 | 中国石油化工股份有限公司 | Methanation process for preparing synthetic natural gas from coal-based synthetic gas |
| CN112759505A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| 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 |
| CN111018671A (en) * | 2020-01-03 | 2020-04-17 | 东华工程科技股份有限公司 | System for synthesizing ethylene glycol by dimethyl oxalate hydrogenation and preparation method thereof |
| 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 |
| 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 |
| CN115646377A (en) * | 2022-11-16 | 2023-01-31 | 陕西延长石油（集团）有限责任公司 | Reaction system and method for continuously producing alpha-alkyl ester |
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