CN102875331B - Heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane - Google Patents
Heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane Download PDFInfo
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- CN102875331B CN102875331B CN201210416602.6A CN201210416602A CN102875331B CN 102875331 B CN102875331 B CN 102875331B CN 201210416602 A CN201210416602 A CN 201210416602A CN 102875331 B CN102875331 B CN 102875331B
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Abstract
The invention relates to a heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane, which is characterized in that hydration reaction is conducted in a high-pressure operated reaction rectifying tower, the separation of reactants and products is conducted in a low-pressure operated stripping tower, a throttle pressure reducing valve and a compressor are arranged between the two towers, liquid mixture at the bottom of the reaction rectifying tower is directly used as liquid for reflux of the stripping tower after the pressure and the temperature of the liquid mixture are reduced through the pressure reducing valve, steam at the top of the stripping tower is directly used as rising steam after the temperature and the pressure of the steam are increased by the compressor, and the final products are obtained from the kettle of the stripping tower. The heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane can realize the effect that the high-temperature and high-pressure reaction and the low-temperature and low-pressure separation are synchronously conducted, and has the advantages of rapid reaction speed, low feed molar ratio of water and epoxy ethane, high epoxy ethane and water conversion, high glycol selectivity and low system energy consumption.
Description
Technical field
The heat pump reactive distillation process that the present invention relates to a kind of hydration of epoxy ethane to prepare ethandiol, belongs to field of chemical technology.
Background technology
Ethylene glycol is a kind of important Organic Chemicals, and Application Areas relates to produces trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc.The industrial method that has multiple production ethylene glycol, wherein hydration of epoxy ethane to prepare ethandiol method is the main method of current industrial employing.The reaction formula of ethylene oxide hydration can be expressed as:
C
2H
4O+H
2O→C
2H
6O
2（EG）
The ethylene glycol (EG) that reaction generates also can continue reaction with oxyethane and generate the byproducts such as Diethylene Glycol (DEG), triethylene glycol.
C
2H
4O+?C
2H
6O
2→C
4H
10O
3（DEG）
C
2H
4O+?C
4H
10O
3→C
6H
14O
4（MEG）
…………
More than the characteristic feature of reaction is: (1) for irreversible parallel-consecutive reaction, reaction will generate the homologue of a series of different ethoxymer distributions; (2) react strong heat release, every moles of ethylene oxide open loop thermal discharge is approximately 100 kJ; (3) boiling-point difference of product is large, oxyethane of every addition generally, and the boiling point of product increases approximately 40 ℃.
It is reported, the ethylene oxide hydration reaction unit in the whole world approximately 70% adopts the technology of SDHe Shell company.This technology adopts (20 ~ 25): 1 water and the raw materials components mole ratio of oxyethane, at 150 ~ 200 ℃, under 0.8 ~ 2.0MPa condition, prepare ethylene glycol, oxyethane transformation efficiency approaches 100%, glycol selectivity 89 ~ 90%, Main By product is Diethylene Glycol and triethylene glycol.The main drawback of this technology is that the charging proportioning of water and oxyethane is high, and in production, a large amount of energy is used for the moisture of evaporation product, and energy consumption is huge, and monoethylene glycol selectivity is on the low side simultaneously.And when adopting (6 ~ 15): 1 low water than time, glycol selectivity can reduce again.Therefore, investigator has actively developed the research of ethylene oxide hydration reaction technology both at home and abroad, and hope can reduce water ring ratio, the reduction separating energy consumption of reaction raw materials and improve the selectivity of ethylene glycol.
Reactive distillation is a kind of emerging chemical process intensifying technology growing up the eighties in last century.This technology in same unit, becomes a representative art of innovation conventional elements operation by PROCESS COUPLING the most key in these two field of chemical engineering of reaction and separation processes, is considered to the pioneer of process intensification.The method that has open source literature report application response rectifying synthesizing glycol, as document < < AIChE J > >, in April, 2008, the 24th volume, the 2nd phase.The document is integrated in hydration reaction and product separation in a reactive distillation column and carries out, and tower arranges conversion zone and stripping section, and water is from the top charging of reactive distillation column, and oxyethane, also can be from reaction zone multistage feeding from the underfeed of conversion zone.The advantage of the method is the charge ratio of water and oxyethane very low (approaching 1), the selectivity high (reaching more than 90%) of ethylene glycol, but when practical application, also there is many difficulties in the method.Such as, the working pressure of the method reactive distillation column is 0.1Mpa, temperature of reaction is 373-393K, and industrial practice shows, and under this condition, ethylene oxide hydration speed of reaction is very slow, and device is difficult to the production capacity that reaches high.And if improve working pressure and the temperature of reaction of tower, the temperature of tower kettle product will improve thereupon, separation difficulty will become the restraining factors that method is implemented.
Chinese patent CN1657514A discloses a kind of reactive distillation process of hydration of epoxy ethane to prepare ethandiol, is characterized in carrying out ethylene oxide hydration reaction two processes separated with ethylene glycol in a reactive distillation column simultaneously.In the method, the raw materials components mole ratio of water and oxyethane is (1. 0 ~ 3.0): 1, and 170 ~ 220 ℃ of temperature of reaction, reaction pressure is counted 0.8 ~ 2.0MPa with absolute pressure.The shortcomings such as it is a lot of that the advantage of this patent technique is that the raw materials components mole ratio of water and oxyethane reduces than tubular reactor, but also have the coupling difficulty of reaction and separation processes, the not high and system energy consumption height of water transformation efficiency.Specifically, in order to improve the speed of reaction of oxyethane, need reactive distillation column to operate under higher pressure and temperature, but this will cause the temperature of tower reactor product to raise, and then cause the rising of reboiler heating medium temperature and the increase of process cost, even can not find economic heating medium.For instance, by the method for this patent (embodiment 3), tower working pressure 1.2Mpa, when the charge ratio of water and oxyethane is 2.8:1, the transformation efficiency that water molar fraction in tower kettle product accounts for about 65%(water is not high, and postorder separating energy consumption is high), tower reactor temperature is 206 ℃.If in the indeclinable situation of pressure, the ratio of expectation water is reduced to 10%, and tower reactor temperature will be over 270 ℃, and this needs expensive heating medium, and its economy is by variation.So how realization response is that the exploitation of ethylene oxide hydration reaction rectification technique needs the key issue solving with separated Optimized Matching.
Summary of the invention
For the not good deficiency of reaction and separation processes coupling in above-mentioned document and patent, the heat-pump-type reactive distillation process that the object of this invention is to provide a kind of hydration of epoxy ethane to prepare ethandiol, can further reduce feed water ratio, improve water transformation efficiency, improve glycol selectivity and reduce the energy consumption of system.
The object of the invention is to solve by the following technical programs:
A kind of heat pump reactive distillation process of hydration of epoxy ethane to prepare ethandiol, it is characterized in that: hydration reaction is carried out in the reactive distillation column of high top pressure operation, reactant and product separation carry out in low voltage operated stripping tower, expenditure and pressure valve and compressor are set between two towers, liquid mixture direct liquid-phase reflux as stripping tower after reducing valve decompression cooling at the bottom of the tower of reactive distillation column, the overhead vapours of stripping tower is the direct rising steam as reactive distillation column after compressor compresses increasing temperature and pressure, system operate continuously, realize high-temperature high-voltage reaction separated with low-temp low-pressure, the finished product obtain from the tower reactor of stripping tower.
Concrete steps of the present invention are as follows:
(a) the high reactants water of boiling point is sent into reactive distillation column from tower top opening for feed, low-boiling oxyethane is sent into reactive distillation column from opening for feed at the bottom of the tower of reactive distillation column, control the charging molar flow of water and oxyethane than being (1-2): 1, the concurrent raw hydration reaction of raw material counter current contact in reactive distillation column, the theoretical plate number of reactive distillation column is 6-20, the working pressure of tower is counted 0.2-2.0 Mpa with absolute pressure, and temperature of reaction is 130-160 ℃;
(b) oxyethane and the water that at reactive distillation column, do not transform completely rise to overhead condenser with gas state under refinery distillation, after circulating water condensation, total reflux enters the top continuation reaction of reactive distillation column, and wherein oxyethane transforms completely in tower;
(c) in reactive distillation column, hydration reaction generates ethylene glycol, Diethylene Glycol and unconverted water leave reaction zone under refinery distillation, from tower reactor discharge port, enter reducing valve, enter stripping tower carry out separation after decompression cooling by pipeline;
(d) stripping tower arranges reboiler, heating medium is water vapor, the theoretical plate number of stripping tower is 6-10, and working pressure is 0.05 ~ 0.2Mpa, preferably atmospheric operation (0.1Mpa), the Heating temperature of tower bottom reboiler is 160-220 ℃, reboil ratio is 4-12, and the finished product that separation obtains are from the extraction of tower reactor discharge port, and stripping tower overhead vapours enters compressor from discharge nozzle, after the intensification degree that boosts, from being arranged on the opening for feed of reactive distillation tower bottom, turn back to reactive distillation column.
Said process carries out continuously, oxyethane and water continuously feeding, and not discharging of tower top, oxyethane transforms completely in tower, and tower reactor product is mainly ethylene glycol, contains a small amount of water and Diethylene Glycol simultaneously.
Technical characteristics and the advantage thereof of technique of the present invention are as follows:
(1) utilize the process intensification means of heat pump reactive distillation, realized the rational Match of High Temperature High Pressure hydration reaction and low-temp low-pressure product separation, can not only guarantee high ethylene oxide hydration speed of reaction, reduced separation costs, its effect is better than and existing reaction and rectifying is integrated in to the reactive distillation process of same tower shell simultaneously.
(2) adopt technique of the present invention, the charging of water and oxyethane mole coupling lower (1 ~ 2): 1, when oxyethane transforms completely in reactive distillation column, the transformation efficiency of water also can reach 90%.Meanwhile, utilize refinery distillation, water forms two circulations at the bottom of the tower top of reactive distillation column and tower, and the ethylene glycol that hydration obtains can leave reaction zone in time, the selectivity that contributes to reduce the generation of side reaction and improve ethylene glycol.
(3) adopt technique of the present invention, do not need to remove hydration reaction heat, reaction heat is directly used in rectifying, has realized the maximum utilization of reaction heat.Meanwhile, adopt the method for low pressure separation to reduce column bottom temperature, can in operating process, adopt the heating medium that temperature is lower, contribute to improve the economy of system.
Accompanying drawing explanation
Fig. 1 is the structural representation of heat pump reaction and rectification device of the present invention.
Wherein: 1 is reactive distillation column, 2 is stripping tower, and 3 is expenditure and pressure valve, 4 is compressor, 5 is condenser, and 6 is oxyethane opening for feed, and 7 is raw water opening for feed, 8 is liquid outlet opening at the bottom of reactive distillation column tower, 9 is reactive distillation column tower spirit phase opening for feed, and 10 is stripping tower liquid phase feeding mouth, and 11 is stripper reboiler, 12 is stripping tower outlet for product, and 13 is stripping tower tower top vapour phase discharge port.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further details, but following examples can not be interpreted as it is limiting the scope of the invention.
embodiment 1
As shown in Figure 1, reactants water enters reactive distillation column (1) from tower top raw water opening for feed (7), and oxyethane is by entering reactive distillation column from reactive distillation column tower base ring oxidative ethane opening for feed (6); In reactive distillation column, first oxyethane contact with water hydration reaction generation high boiling component ethylene glycol (EG) occur, and the ethylene glycol of generation also will generate the Diethylene Glycol that boiling point is higher (DEG) with reacting ethylene oxide; At the oxyethane not transforming completely in tower and water, under refinery distillation, with gas state, rise to tower top and after overhead condenser (5) condensation, turn back to continuation reaction in tower, high boiling component EG, the DEG and the unconverted water that generate leave reaction zone under refinery distillation, from liquid outlet opening (8) at the bottom of reactive distillation column tower, enter expenditure and pressure valve (3), after decompression cooling, by stripping tower liquid phase feeding mouth (10), enter stripping tower (2) and carry out separation; Stripping tower arranges reboiler (11), heating medium is water vapor, the finished product that separation obtains are from stripping tower outlet for product (12) extraction, stripping tower overhead vapours enters compressor (4) from tower top vapour phase discharge port (13), after the intensification degree that boosts, from being arranged on reactive distillation column tower spirit phase opening for feed (9), turn back to reactive distillation column (1).
The equipment of tower and structural parameter are: reactive distillation column arranges 7 blocks of column plates, water opening for feed is arranged on the 2nd plate top, epoxyethane water opening for feed is arranged on the 5th plate top, stripping tower arranges 5 blocks of column plates, liquid inlet opening is arranged on the 1st plate top, and top gaseous phase discharging turns back on the 6th block of plate of reactive distillation column after compressor.
The operational condition of reactive distillation column is: water feed rate is 26.30kmol/h, and oxyethane feed rate is 25.00 kmol/h, and water and oxyethane charging molar flow are than being 1.05:1.00, and working pressure is 0.40MPa, and tower top temperature is 144.20 ℃.
The operational condition of stripping tower is: working pressure is 0.10MPa, and tower top temperature is 101.00 ℃, and tower reactor temperature is 164.00 ℃, steam heating, and reboiler operation reboil ratio is 9.
The operating parameters of expenditure and pressure valve and compressor is: reducing valve top hole pressure is 0.10Mpa, and compressor power is 1049.60 kW, and compressor delivery pressure is 0.41 MPa.
At the bottom of stripping tower tower, extraction liquid product adopts chromatogram to analyze its composition after cooling.
Molar product consists of: oxyethane do not detected, and water 11.50%, ethylene glycol 82.00%, Diethylene Glycol 6.51%, does not detect the product of triethylene glycol and higher adduct number.As calculated, oxyethane transformation efficiency 99.99%, water transformation efficiency 88.50%, ethylene glycol is 82.00% to the selectivity of oxyethane.
embodiment 2
The equipment of tower and structural parameter are identical with embodiment 1.
The operational condition of reactive distillation column is: water feed rate is 25.00 kmol/h, and oxyethane feed rate is 25.00kmol/h, and water and oxyethane charging molar flow are than being 1:1, and working pressure is 0.40MPa, and tower top temperature is 144.00 ℃.
The operational condition of stripping tower is: working pressure is 0.10MPa, and tower top temperature is 101.00 ℃, and tower reactor temperature is 176.00 ℃, steam heating, and reboiler operation reboil ratio is 10.
The operating parameters of expenditure and pressure valve and compressor is: reducing valve top hole pressure is 0.10Mpa, and compressor power is 1046.80 kW, and compressor delivery pressure is 0.41 MPa.
At the bottom of stripping tower tower, extraction liquid product adopts chromatogram to analyze its composition after cooling.
Molar product consists of: oxyethane do not detected, and water 6.88%, ethylene glycol 86.30%, Diethylene Glycol 6.88%, does not detect the product of triethylene glycol and higher adduct number.As calculated, oxyethane transformation efficiency 99.99%, water transformation efficiency 93.12%, ethylene glycol is 86.30% to the selectivity of oxyethane.
embodiment 3
The equipment of tower and structural parameter are identical with embodiment 1.
The operational condition of reactive distillation column is: water feed rate is 26.30kmol/h, and oxyethane feed rate is 25.00kmol/h, and water and oxyethane charging molar flow are than being 1.05:1; Working pressure is 0.30MPa, and tower top temperature is 134.00 ℃.
The operational condition of stripping tower is: working pressure is 0.05MPa, and tower top temperature is 83.00 ℃, and tower reactor temperature is 142.00 ℃, steam heating, and reboiler operation reboil ratio is 9.
The operating parameters of expenditure and pressure valve and compressor is: reducing valve top hole pressure is 0.05Mpa, and compressor power is 1357.90 kW, and compressor delivery pressure is 0.31 MPa.
At the bottom of tower, extraction liquid product adopts chromatogram to analyze its composition after cooling.
Bottom product mole consists of: oxyethane do not detected, and water 11.20%, ethylene glycol 82.50%, Diethylene Glycol 6.28%, does not detect the product of triethylene glycol and higher adduct number.As calculated, oxyethane transformation efficiency reaches 99.99%, water transformation efficiency 88.80%, and ethylene glycol is 82.50% to the selectivity of oxyethane.
Claims (8)
1. the heat pump reactive distillation process of a hydration of epoxy ethane to prepare ethandiol, it is characterized in that, hydration reaction is carried out in the reactive distillation column (1) of high top pressure operation, reactant and product separation carry out in low voltage operated stripping tower (2), expenditure and pressure valve (3) and compressor (4) are set between two towers, at the bottom of the tower of reactive distillation column (1) liquid mixture after expenditure and pressure valve (3) decompression cooling directly as the liquid-phase reflux of stripping tower (2), the overhead vapours of stripping tower after compressor (4) compression increasing temperature and pressure directly as the rising steam of reactive distillation column (1), system operate continuously, realize high-temperature high-voltage reaction separated with low-temp low-pressure, the finished product obtain from the tower reactor of stripping tower (2), described reactive distillation column (1) arranges condenser (5), reboiler is not set, oxyethane is from being arranged on opening for feed (6) charging of tower bottom, water is from being arranged on opening for feed (7) charging on tower top, overhead vapours is all got back to the top of tower after condenser (5) condensation, hydration reaction product and unconverted water enter expenditure and pressure valve (3) from discharge port (8) extraction at the bottom of being arranged on tower, and the vapor-phase product of compressor (4) outlet turns back to reactive distillation column (1) from being arranged on the vapour phase opening for feed (9) of reactive distillation tower bottom, described stripping tower (2) arranges reboiler (11), the liquid mixture that leaves expenditure and pressure valve (3) enters stripping tower and carries out separation from being arranged on the opening for feed (10) on tower top, the finished product are from tower reactor discharge port (12) extraction, and stripping tower overhead vapours enters compressor from discharge port (13).
2. technique according to claim 1, is characterized in that the working pressure of described reactive distillation column is higher than stripping tower, and hydration reaction is carried out in the reactive distillation column of High Temperature High Pressure, in the stripping tower that is separated in low-temp low-pressure of reactant and product, carries out.
3. technique according to claim 1, the working pressure that it is characterized in that described reactive distillation column is counted 0.2 ~ 2.0 MPa by absolute pressure, the working pressure of stripping tower is counted 0. 05 ~ 0.2 Mpa by absolute pressure, top hole pressure and the stripping tower of reducing valve liquid phase material match, and top hole pressure and the reactive distillation column of compressor vapor-phase material match.
4. technique according to claim 1, is characterized in that in described reactive distillation column that oxyethane and water molar feed ratio are 1:(1 ~ 2).
5. technique according to claim 1, the reboiler reboil ratio that it is characterized in that described stripping tower is 4 ~ 12.
6. technique according to claim 1 and 2, the pattern that it is characterized in that described reactive distillation column and stripping tower is tray column or packing tower.
7. technique according to claim 1, the theoretical plate number that it is characterized in that described reactive distillation column is 6 ~ 20, the theoretical plate number of stripping tower is 6 ~ 10.
8. technique according to claim 1, is characterized in that described hydration reaction is catalytic hydration or on-catalytic hydration.
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|---|---|---|---|
| CN201210416602.6A CN102875331B (en) | 2012-10-28 | 2012-10-28 | Heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane |
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| CN201210416602.6A CN102875331B (en) | 2012-10-28 | 2012-10-28 | Heat pump reaction rectification technology for preparing glycol through hydration of epoxy ethane |
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| ES2729155T3 (en) * | 2015-12-16 | 2019-10-30 | Repsol Sa | Method for the preparation of glycols |
| CN107602374B (en) * | 2017-10-09 | 2019-10-15 | 福州大学 | A method of carboxylic acid is separated based on ethylene oxide hydration reactive distillation |
| CN109745724B (en) * | 2019-01-24 | 2021-04-23 | 山东伯仲真空科技股份有限公司 | MVR (mechanical vapor recompression) rectification and stripping composite device and process method thereof |
| CN115105851B (en) * | 2022-07-15 | 2024-04-16 | 中国石油化工股份有限公司 | Separation process and separation device for sulfuric acid alkylation reaction product |
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| KR20000048902A (en) * | 1996-10-04 | 2000-07-25 | 그레이스 스티븐 에스. | A method for producing glycols |
| CN1268594C (en) * | 2004-02-18 | 2006-08-09 | 中国石油化工股份有限公司 | Method of preparing ethylene glycol |
| CN100413833C (en) * | 2004-04-16 | 2008-08-27 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing glycol by epoxy ethane hydration |
| CN101121640A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by catalysis rectification |
| CN102040473B (en) * | 2009-10-13 | 2013-12-25 | 中国石油化工股份有限公司 | Method for producing ethylene glycol |
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