CN105037094B - A kind of energy coupling rectificating method of acetate preparation of ethanol by hydrogenating - Google Patents
A kind of energy coupling rectificating method of acetate preparation of ethanol by hydrogenating Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
A kind of energy coupling rectificating method of acetate preparation of ethanol by hydrogenating, crude glycol with the preparation of acetate hydrogenation technique is as raw material, by lightness-removing column, methanol column, ethanol tower three-tower rectification and energy coupling, the very high methanol product of purity and alcohol product can be obtained, simultaneously, lightness-removing column tower top light component can return to acetic acid ester through hydrogenation workshop section circular response, to reach maximum light component utilization rate.Energy coupling is under the conditions of lightness-removing column normal pressure, methanol column malleation, ethanol tower negative pressure or atmospheric operation, heat supply lightness-removing column tower bottoms is condensed using methanol column tower overhead gas and ethanol tower tower bottoms is boiling hot again, reduce the consumption of cooling medium and heating medium simultaneously, greatly reduce the energy consumption of device.
Description
First, technical field
The present invention relates in separating technology and separation process in a kind of chemical process energy utilization method, definitely
For be a kind of energy coupling rectificating method of acetate preparation of ethanol by hydrogenating.
2nd, background technology
Ethanol, is commonly called as alcohol, is volatile liquid that is a kind of colourless and having peat-reek under room temperature.Ethanol is inflammable, is normal
Fuel, solvent and disinfectant；Used as a kind of important basic chemical industry raw material, it is widely used in food, chemical industry, army
The numerous areas such as work, medicine.
Industrial general use amylo process or ethylene hydration method ethanol production.Recently as the rise of Coal Chemical Industry, coal
Ethanol processed gradually enters into the visual field.Coal ethanol refer to coal as raw material through gasification as synthesis gas or with plant gas (mainly into
Divide and be CO and H2) it is raw material, using the process of different process route production ethanol.At present, ethanol is produced as source with coal
Process route mainly have four；See Fig. 2.
From the point of view of reaction mechanism, direct method path is shorter, but due to its CO conversion ratio low, the selectivity of ethanol and raw material profit
Relatively low with rate, it is mostly in the experimental study stage at present, rarely has the report of commercial Application.Although indirect method path is longer, former
The selectivity of the conversion ratio and ethanol of material has reached higher level, for the research of catalyst and course of reaction has also reached
To the stage that large-scale commercial is promoted, have large-scale industry device at present and building.
The advantage of acetic acid direct hydrogenation legal system ethanol is：Path is relatively short；Investment yield is higher.Inferior position is：Mostly
Using noble metal catalyst, high cost；Acetic acid raw material reaction conversion ratio does not reach 100%, equipment material is required higher；Reaction
There is water to produce, separating energy consumption is higher.
Acetic acid esterified hydrogenation legal system ethanol solves the subject matter of directed hydrogenation presence, and its advantage is：Using non-noble
Metallic catalyst, cost are relatively low；Equipment material is required relatively low；Anhydrous generation is reacted, separating energy consumption is relatively low.Inferior position is：Many one
Step esterification, reaction process are longer.
Ethanol can rough segmentation be absolute ethyl alcohol (ethanol mass fraction >=99.5%), industrial alcohol (ethanol mass fraction >=
95%), the different stage such as alcohol fuel (ethanol mass fraction >=92.1%), can adopt different separation according to different specifications
Technique.
Crude glycol of the present invention refers to methyl acetate (lower abbreviation acetate) Hydrogenation second under Cu-series catalyst effect
The crude glycol product that alcohol is directly obtained, in the mixture, each component is as follows：
| Material | Ethanol | Methyl alcohol | Acetate | Remaining trace impurity |
| Mass fraction/% | 30～70 | 30～70 | 0.1～10 | Propyl alcohol, water etc. |
Remarks：Minor amount of water is to bring water in raw material, and hydrogenation reaction itself is without water generating.
3rd, content of the invention
It is an object of the invention to the crude glycol product directly obtained by rectification process Dichlorodiphenyl Acetate ester through hydrogenation ethanol is carried out
Separate, on the one hand obtain product methyl alcohol, ethanol, on the other hand reclaim light component acetate and recycle.Technology to be solved
Problem is reducing the energy consumption of device by energy coupling.
Rectifying of the present invention is that three tower apparatus being made up of lightness-removing column, methanol column and ethanol tower carry out three-tower rectification,
Detailed process is as follows：
Crude glycol initially enters lightness-removing column, after separating through lightness-removing column, mixed vapour of the top gaseous phase for acetate and methyl alcohol etc.；
After through condenser of light component removal column condensation, a part of condensate liquid returns lightness-removing column overhead reflux, and another part is light based on acetate
Component returns upstream acetic acid ester through hydrogenation workshop section, reclaims circulation hydrogenation and utilizes；Tower reactor is the ethanol containing minor amount of water, propyl alcohol etc., first
Mixed alkoxide solution, is pumped into methanol column and is separated.
The operating pressure of lightness-removing column (1) be normal pressure, tower top temperature 55-65 DEG C, 65-75 DEG C of bottom temperature, reflux ratio 1-50.
After separating through methanol column, top gaseous phase is methyl alcohol；After through the condensation of methanol column condenser, a part of condensate liquid returns first
Alcohol column overhead flows back, and another part removes product storage tank as methanol product (mass fraction >=99.9%) extraction；Tower reactor be containing
The ethanol solution (mass fraction >=98%) of minor amount of water, propyl alcohol etc., is pumped into ethanol tower and further separates.
The operating pressure of methanol column (2) is 0.2-0.8MPa, and tower top temperature 80-130 DEG C, 100-150 DEG C of bottom temperature are returned
Stream compares 1-30.
After separating through ethanol tower, top gaseous phase is ethanol (mass fraction >=99.5%) and water (mass fraction≤0.5%)
Mixed vapour；After through the condensation of ethanol tower condenser, a part of condensate liquid returns ethanol tower overhead reflux, and another part is used as second
Product storage tank is removed in the extraction of alcohol product；Tower reactor is the heavy constituent solution containing micro propyl alcohol etc..
Negative pressure or normal pressure of the operating pressure of ethanol tower (3) for 0.01-0.09MPa, tower top temperature 40-90 DEG C, tower reactor temperature
50-100 DEG C of degree, reflux ratio 1-30.
Energy coupling rectificating method alleged by the present invention is in lightness-removing column normal pressure, methanol column malleation, ethanol tower normal pressure or negative
Under the conditions of press operation, the boiling hot again of heat supply lightness-removing column and ethanol tower tower bottoms is condensed using methanol column overhead vapours, to realize
The energy coupling of rectification working process, reducing energy consumption.Concrete grammar is as follows：
Before methanol column is arranged on due to lightness-removing column, so first, second two reboilers need to be set in lightness-removing column tower reactor,
Using the first reboiler, steam heating during driving；Using the second reboiler during normal operating, supplied by methanol column tower overhead gas gas phase
Heat, for this purpose, the second reboiler is with one loop of composition between the tower top and methanol column condenser of methanol column.
Heat exchanger is set between lightness-removing column tower reactor and methanol column tower reactor, the tower bottoms of light device is taken off through heat exchanger pre-heating temperature elevation
After be pumped into methanol column；The tower bottoms of methanol column is pumped into ethanol tower after heat exchanger heat exchange.
In methanol column tower reactor, the 3rd reboiler, steam heating are set.
4th reboiler is set in ethanol tower reactor, the 4th reboiler is with structure between the tower top and methanol column condenser of methanol column
Into a loop, by methanol column tower overhead gas gas phase heat supply, realize heating ethanol tower tower bottoms, so as to omit steam confession
Heat.
Described reboiler is exactly heat exchanger, can be the conventional heat exchanger such as shell and tube or coiled.
This method is taken into full account recycling for light component, is made using de- light, methanol column, three tower joint operation of ethanol tower
The unconverted acetate of one way after lightness-removing column is separated returns to upstream and is hydrogenated with workshop section.The methanol product of higher degree is obtained simultaneously
(mass parts >=99%) and alcohol product (mass parts >=99.2%).
This method takes into full account the comprehensive utilization of energy, achieves the energy of methanol column and lightness-removing column and ethanol tower well
Coupling；The circulation water consumption of ton product ethanol saves at least 200 tons, and steam consumption saves at least 2.5 tons.
4th, illustrate
Schematic flow sheets of the Fig. 1 for this method.
In figure：1. lightness-removing column, 2. methanol column, 3. ethanol tower, 4. condenser of light component removal column, 5. the second reboiler, 6. first again
Device is boiled, 7. methyl alcohol device condenser, 8. the 3rd reboiler, 9. ethanol tower condenser, 10. the 4th reboiler, 11. heat exchangers, 12. first
Alcohol tower feed pump, 13. ethanol tower feed pumps.
Fig. 2 is four process route charts for producing ethanol with coal as source.
Five. specific embodiment
1. three tower apparatus
Lightness-removing column tower top has condenser of light component removal column；Tower reactor is provided with first, second reboiler, the former steam heating, Hou Zheyou
Methyl alcohol tower overhead gas gas phase heat supply, and between the tower top with methanol column and methanol column condenser, constitute a loop.
Methyl alcohol column overhead has methanol column condenser；Tower reactor is provided with the 3rd reboiler, steam heating.In methanol column tower reactor and de-
Heat exchanger is provided between light tower tower reactor；Lightness-removing column tower bottoms enters methanol column through heat exchanger after methanol column feed pump again,
Methanol column tower bottoms enters ethanol tower through heat exchanger.
Ethanol column overhead has ethanol tower condenser；Tower reactor is provided with the 4th reboiler, the reboiler with methanol column tower top with
A loop is constituted between methanol column condenser.
2. three-tower rectification
The crude glycol that workshop section is hydrogenated with from upstream acetic acid initially enters lightness-removing column, after separating through lightness-removing column, top gaseous phase
After (predominantly methyl alcohol and acetate) is through condenser of light component removal column condensation, a part of condensate liquid returns lightness-removing column tower top and returns
Stream, another part return upstream acetic acid ester through hydrogenation workshop section as light component；Tower reactor be coarse ethanol, methyl alcohol mixed solution through heat exchanger
After pre-heating temperature elevation, pumping methanol column is separated.The operating pressure of lightness-removing column (1) be normal pressure, tower top temperature 55-65 DEG C, tower reactor temperature
65-75 DEG C of degree, reflux ratio 1-50.
After separating through methanol column, after top gaseous phase is through methanol condenser condensation, a part of condensate liquid returns methyl alcohol column overhead
Backflow, another part remove product storage tank as methanol product extraction；Tower reactor is coarse ethanol solution, is pumped into after heat exchanger heat exchange
Ethanol tower is further separated.
The operating pressure of methanol column (2) is 0.2-0.8MPa, and tower top temperature 80-130 DEG C, 100-150 DEG C of bottom temperature are returned
Stream compares 1-30.
After separating through ethanol tower, after top gaseous phase is through the condensation of ethanol tower condenser, a part of condensate liquid returns ethanol tower tower
Top backflow, another part remove product storage tank as alcohol product extraction：Tower reactor obtains a small amount of heavy constituent solution, and main component is third
Alcohol and 2- butanol, yield very little, used as byproduct interruption extraction.
Negative pressure or normal pressure of the operating pressure of ethanol tower (3) for 0.01-0.09MPa, tower top temperature 40-90 DEG C, tower reactor temperature
50-100 DEG C of degree, reflux ratio 1-30.
3. energy coupling
Lightness-removing column arrange two reboilers, using the first reboiler during driving, using steam heating, tower bottoms is carried out plus
Heat, using the second reboiler during normal operating, using methanol column tower overhead gas gas phase heat supply.
Methanol column tower reactor arranges the 3rd reboiler, and steam heating proceeds to heating to tower bottoms.In methanol column tower reactor and de-
Heat exchanger is set between light tower tower reactor, realizes the heat exchange of lightness-removing column tower bottoms and methanol column tower bottoms.
Ethanol tower tower reactor to be arranged and constitute loop between the 4th reboiler, and the tower top with methanol column and methanol column condenser,
Using methanol column tower overhead gas gas phase heat supply.
Claims (1)
1. a kind of energy coupling rectificating method of acetate preparation of ethanol by hydrogenating, it is characterised in that：Prepared with acetate hydrogenation technique
Crude glycol be raw material, three towers being made up of lightness-removing column (1), methanol column (2) and ethanol tower (3) carry out three-tower rectification and energy coupling
Close, which comprises the following steps that：
(1) three-tower rectification
A. crude glycol initially enters lightness-removing column (1) and is separated, and top gaseous phase is the mixed vapour of acetate and methyl alcohol；Through lightness-removing column
After condenser (4) condensation, a part of condensate liquid backflow, another part return upstream acetic acid ester through hydrogenation workshop section；Tower bottoms is pumped into
Enter methanol column (2) to be separated；
The operating pressure of lightness-removing column (1) be normal pressure, tower top temperature 55-65 DEG C, 65-75 DEG C of bottom temperature, reflux ratio 1-50；
B., after separating through methanol column (2), top gaseous phase is methyl alcohol；After through methanol column condenser (7) condensation, a part of condensate liquid is returned
Stream, another part remove product storage tank as methanol product extraction；Tower bottoms is pumped into ethanol tower (3) and further separates；
The operating pressure of methanol column (2) be 0.2-0.8MPa, tower top temperature 80-130 DEG C, 100-150 DEG C of bottom temperature, reflux ratio
1-30；
C., after separating through ethanol tower (3), top gaseous phase is ethanol；After through ethanol tower condenser (9) condensation, a part of condensate liquid is returned
Stream, another part remove product storage tank as alcohol product extraction；Tower bottoms interruption extraction；
Negative pressure or normal pressure of the operating pressure of ethanol tower (3) for 0.01-0.09MPa, tower top temperature 40-90 DEG C, bottom temperature 50-
100 DEG C, reflux ratio 1-30；
(2) energy coupling
Under the conditions of lightness-removing column (1) normal pressure, methanol column (2) malleation, ethanol tower (3) negative pressure or atmospheric operation, using methanol column tower
Top steam condensation heat supply lightness-removing column (1) tower bottoms and ethanol tower (3) tower bottoms are boiling hot again, and concrete grammar is as follows：
Lightness-removing column (1) tower reactor arranges two reboilers (5), (6), using the first reboiler (6), steam heating during driving；Normally
Using the second reboiler (5) by the gas phase heat supply of methanol column (2) tower overhead gas during operation, reboiler (5) with methanol column tower top with cold
A loop is constituted between condenser (7)；
Heat exchanger (11) is set between lightness-removing column (1) tower reactor and methanol column (2) tower reactor, and the tower bottoms of lightness-removing column (1) is through heat exchange
Methanol column (2) is entered after device (11) preheating, the tower bottoms of methanol column (2) is changed through ethanol tower feed pump (13) and heat exchanger (11)
Ethanol tower (3) is entered after heat；
Ethanol tower (3) tower reactor arranges the 4th reboiler (10), and reboiler (10) is with structure between the tower top and condenser (7) of methanol column
Into a loop.
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| CN105693468B (en) * | 2016-03-22 | 2017-03-08 | 凯凌化工(张家港)有限公司 | Isopropyl acetate hydrogenization method production ethanol and the post-processing approach of isopropanol |
| CN106554253B (en) * | 2016-11-08 | 2019-06-18 | 西南化工研究设计院有限公司 | A kind of product separated energy-saving technique of acetate preparation of ethanol by hydrogenating |
| CN106588572B (en) * | 2017-01-23 | 2023-08-22 | 神华集团有限责任公司 | Three-tower differential pressure coupling rectification system and method for separating low-carbon mixed alcohol |
| CN108079610B (en) * | 2018-01-15 | 2024-02-23 | 苏州欧拉透平机械有限公司 | Energy-saving methanol rectifying device and rectifying method thereof |
| CN108299157A (en) * | 2018-01-29 | 2018-07-20 | 安徽皖维高新材料股份有限公司 | A method of preparing ethyl alcohol using calcium carbide stove exhaust |
| CN111423308B (en) * | 2019-01-10 | 2023-03-28 | 惠生工程（中国）有限公司 | Product separation system and separation method for preparing ethanol by methyl acetate hydrogenation |
| CN110498736A (en) * | 2019-09-19 | 2019-11-26 | 天津中科拓新科技有限公司 | A kind of benzyl alcohol adds hydrogen to prepare the process of cyclohexanemethanol |
| CN115707679B (en) * | 2021-08-19 | 2024-01-05 | 北京石油化工工程有限公司 | Separation method and system for preparing crude product of ethanol by methyl acetate hydrogenation |
| CN115707680B (en) * | 2021-08-19 | 2024-01-30 | 北京石油化工工程有限公司 | Progressive separation method and system for preparing crude product of ethanol by methyl acetate hydrogenation |
| CN114478193B (en) * | 2022-01-06 | 2024-04-30 | 北京泽华化学工程有限公司 | Separation method and separation device for preparing ethanol from dimethyl ether |
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| CN103387481A (en) * | 2013-08-06 | 2013-11-13 | 上海华谊（集团）公司 | Method for producing ethanol through acetic acid esterification-hydrogenation |
| CN103739443A (en) * | 2014-01-21 | 2014-04-23 | 上海华谊（集团）公司 | Method for cogeneration ethanol and methanol employing synthesis gas and ethyl acetate reaction |
| CN104649862B (en) * | 2015-02-05 | 2016-10-05 | 天津大学 | With ethyl acetate be raw material production alcohol product method and equipment |
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