CN107573214A - The method that ethanol is prepared with methanol - Google Patents
The method that ethanol is prepared with methanol Download PDFInfo
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- CN107573214A CN107573214A CN201710839160.9A CN201710839160A CN107573214A CN 107573214 A CN107573214 A CN 107573214A CN 201710839160 A CN201710839160 A CN 201710839160A CN 107573214 A CN107573214 A CN 107573214A
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Abstract
A kind of method that ethanol is prepared with methanol, comprises the following steps：Methanol feedstock reacts after vaporization with water vapour into methanol converter, and reformed gas is made；The purified tower of reformed gas is purified, and obtains pure hydrogen；Steam after hydrogen vaporizes with ethyl acetate is mixed, and enters reactor reaction, produces coarse ethanol；Coarse ethanol enters rectifying column and carries out runoff operation, obtains qualified alcohol product.This method that ethanol is prepared with methanol, ethanol is added mainly for the production of as the gasoline of fuel, process is simple, easy to operate, carrying out simple operations using existing equipment can complete to produce, and production efficiency is high, alcohol product concentration made from production is high, the requirement of the alcohol fuel as gasoline additive is complied fully with, cost is low, and effect is good.
Description
Technical field
The present invention relates to a kind of preparation method of ethanol, specifically a kind of method that ethanol is prepared using methanol.
Background technology
In recent years, serious energy crisis is faced in global range, find new fungible energy source turns into various countries' future
The key of energy strategy.Among these, ethanol has the characteristics that renewable, efficient, low consumption provides, be safe, and ethanol, can be straight as fuel
Connect as liquid fuel or be used in mixed way with gasoline, reduce the dependence to this non-renewable energy resources of oil, so as to ensure this
The safety of state's energy.
Traditional ethanol preparation method is by the fermentation to cereal, potato class and saccharine material, distillation, is realized continuous raw
Producing and ethanol, this traditional method for preparing ethanol is less efficient, and purity is poor, big by concentration of alcohol caused by simple distillation
More not over 96% (V/V).As gasoline, the alcohol fuel of the effective additive of diesel oil, its concentration of alcohol must be not less than 99.5%
(W/W).Therefore, the current conventional art for preparing ethanol, it is impossible to meet the requirement of high concentration ethanol.
Patent document 200880127691.4 discloses a kind of method that ethanol is prepared with methanol, described in the patent document
Method for converting methanol into ethanol, including：
（a）In the presence of the salt of active metal, or in the presence of the active metal that simultaneously slurry crushes is ground, by methanol and one
Carbonoxide reacts to prepare the product for including at least 25 moles % methyl acetates in the liquid phase；With
（b）The methyl acetate is hydrogenated with to prepare ethanol, wherein the active metal is VIII races metal.
Wherein play leading role is the salt of active metal, and the active metal is applied in combination with co-catalyst.
Co-catalyst is methyl halide.Co-catalyst is green co-catalyst, and the green co-catalyst is carbonic acid
Dimethyl ester.That is, preparation method disclosed in the patent needs to complete in the presence of active metal, and need to add
Co-catalyst, not only complex steps are, it is necessary to add actual reaction condition requirement harsher, and it is feasible to carry out laboratory operation,
But for large-scale alcohol production producer, oneself input of original material agent is not only increased, and reaction environment requires severe
Carve, be not easy to realize.
The content of the invention
The problem of existing for prior art, the present invention provide one kind and utilize methanol hydrogen making, then by with acetic acid second
Ester carries out hydrogenation reaction and obtains the method for ethanol, and ethanol made from this method uses mainly as gasoline addition ethanol.
Realize that foregoing invention purpose uses following technical scheme：
A kind of method that ethanol is prepared with methanol, comprises the following steps：
（a）Methanol feedstock reacts after vaporization with water vapour into methanol converter, and reformed gas is made；
（b）Step（a）The obtained purified tower of reformed gas is purified, and obtains pure hydrogen；
（c）Step（b）Steam after obtained hydrogen vaporizes with ethyl acetate is mixed, and enters reactor reaction, is produced
Coarse ethanol；
（d）Step（c）Obtain coarse ethanol and carry out runoff operation into rectifying column, obtain qualified alcohol product.
Described methanol feedstock is the liquid methanol for meeting GB338-2011 requirements.
Step（a）In, methanol feedstock presses 1 after heat exchange vaporizes, with water vapour:1 mass ratio is mixed.
Mixed methanol feedstock exchanges heat to after 220-240 DEG C again with water vapour, into reactor reaction, enters again afterwards
Row cooling separation.
Step（a）In obtained reformed gas be to mainly contain the mixed gas of hydrogen and carbon dioxide.
Step（b）In, after reformed gas enters purifying column, obtain the purified hydrogen of content >=99.98%.
Step（c）In, the steam after hydrogen and ethyl acetate vaporization is pressed 40:1 mass ratio mixing, mixed gas
Enter reactor after vaporizer, superheater are preheated to 180-190 DEG C, carry out being hydrogenated with instead under 3.0-3.3Mpa pressure environment
Coarse ethanol should be obtained.
Step（d）In, alcohol product is obtained as absolute alcohol of the weight/mass percentage composition more than 99.5% by rectifying.
Step（b）In, the ethyl acetate is weight/mass percentage composition ＞ 99.9% liquid.
This method that ethanol is prepared with methanol disclosed in this invention, added mainly for the production of as the gasoline of fuel
Ethanol, process is simple, easy to operate, and carrying out simple operations using existing equipment can complete to produce, and production efficiency is high, production system
The alcohol product concentration obtained is high, complies fully with the requirement of the alcohol fuel as gasoline additive, cost is low, and effect is good.
Brief description of the drawings
Fig. 1 is the technological process simplified schematic diagram of the present invention.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
The method that ethanol is prepared with methanol, comprises the following steps.
（a）Methanol feedstock reacts after vaporization with water vapour into methanol converter, and reformed gas, the reformed gas is made
It is the mixed gas for mainly containing hydrogen and carbon dioxide.Methanol feedstock is the liquid methanol of compound GB338-2011 requirements.
（b）Step（a）The obtained purified tower of reformed gas is purified, and obtains pure hydrogen, the content of the hydrogen
≥99.98%.Methanol feedstock presses 1 after heat exchange vaporizes, with water vapour:1 mass ratio is mixed.Mixed methanol feedstock
Exchanged heat again to after 220-240 DEG C with water vapour, into reactor reaction, carry out cooling separation again afterwards.
（c）Step（b）Steam after obtained hydrogen vaporizes with ethyl acetate is mixed, and it is anti-together to enter reactor
Should, produce coarse ethanol.Ethyl acetate is weight/mass percentage composition ＞ 99.9% liquid.By the steaming after hydrogen and ethyl acetate vaporization
Vapour presses 40:1 mass ratio mixing, enters reactor, in 3.0-3.3Mpa after vaporizer, superheater are preheated to 180-190 DEG C
Pressure environment under carry out hydrogenation reaction obtain coarse ethanol.
（d）Step（c）Obtain coarse ethanol and carry out runoff operation into rectifying column, obtain qualified alcohol product.By rectifying
Obtain the absolute alcohol that alcohol product is more than 99.5% for weight/mass percentage composition.
Embodiment 1
Methanol liquid as raw material is passed into converter after overflash, and is 1 according to methanol vapor and vapor:1
Mass ratio be passed through middle pressure steam mixing, methanol converter is entered after being warming up to 240 DEG C.Temperature environment is maintained at 240 DEG C
Converter in carry out gas phase catalytic reaction, while complete catalytic pyrolysis and conversion two reaction, obtained after refrigerated separation
The reformed gas of main hydrogen and carbon dioxide.Reformed gas enters after hydrogen purification tower obtains content 99.8% by purification
Above hydrogen.Hydrogen by purification is carried out mixing vaporization with ethyl acetate steam, and it is anti-that 190 DEG C of entrance are warming up to after heat exchange
Device is answered, it is anti-that ethyl acetate hydrogenation is carried out in the environment of 200 DEG C of temperature, pressure 3.0-3.3MPa, under the conditions of copper-zinc system catalyst
Should, the coarse ethanol of generation cools down after heat exchange to be separated with excess hydrogen, and hydrogen recycles into circulating hydrogen compressor, thick second
Alcohol enters rectifying column and carries out distillation operation, obtains qualified gasoline addition alcohol product.
Ethanol by ethyl acetate hydrogenation production is due to the extremely low only 0.1%-0.2% of water content, after distillation operation
It can obtain qualified ethanol petrol, it is not necessary to considering 95% ethanol azeotrope with water problem.
Claims (9)
1. a kind of method that ethanol is prepared with methanol, it is characterized in that, comprise the following steps：
（a）Methanol feedstock reacts after vaporization with water vapour into methanol converter, and reformed gas is made；
（b）Step（a）The obtained purified tower of reformed gas is purified, and obtains pure hydrogen；
（c）Step（b）Steam after obtained hydrogen vaporizes with ethyl acetate is mixed, and enters reactor reaction, is produced
Coarse ethanol；
（d）Step（c）Obtain coarse ethanol and carry out runoff operation into rectifying column, obtain qualified alcohol product.
2. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Described methanol feedstock is to meet
The liquid methanol of GB338-2011 requirements.
3. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（a）In, methanol feedstock is through changing
After hot vapour, 1 is pressed with water vapour:1 mass ratio is mixed.
4. the method according to claim 3 that ethanol is prepared with methanol, it is characterized in that：Mixed methanol feedstock steams with water
Vapour exchanges heat to after 220-240 DEG C again, into reactor reaction, carries out cooling separation again afterwards.
5. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（a）In obtained conversion gas
Body is the mixed gas for mainly containing hydrogen and carbon dioxide.
6. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（b）In, reformed gas enters
After purifying column, the purified hydrogen of content >=99.98% is obtained.
7. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（c）In, by hydrogen and acetic acid
Steam after ethyl ester vaporization presses 40:1 mass ratio mixing, mixed gas are preheated to 180-190 DEG C through vaporizer, superheater
Enter reactor afterwards, hydrogenation reaction is carried out under 3.0-3.3Mpa pressure environment and obtains coarse ethanol.
8. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（d）In, obtained by rectifying
Alcohol product is the absolute alcohol that weight/mass percentage composition is more than 99.5%.
9. the method according to claim 1 that ethanol is prepared with methanol, it is characterized in that：Step（b）In, the ethyl acetate
For weight/mass percentage composition ＞ 99.9% liquid.
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| CN201710839160.9A CN107573214A (en) | 2017-09-18 | 2017-09-18 | The method that ethanol is prepared with methanol |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155511A (en) * | 1996-01-22 | 1997-07-30 | 中国石化齐鲁石油化工公司 | Process and apparatus for converting methanol vapor into hydrogen |
| CN101965324A (en) * | 2008-02-28 | 2011-02-02 | 埃讷肯公司 | Production of ethanol from methanol |
| CN102766021A (en) * | 2012-07-24 | 2012-11-07 | 唐山市冀东溶剂有限公司 | Production system and production method for continuously producing ethanol by ethyl acetate through using hydrogenation |
| CN104555922A (en) * | 2015-01-23 | 2015-04-29 | 成都科特瑞兴科技有限公司 | New technology for producing hydrogen by conversion of methyl alcohol and water vapor |
| CN105669379A (en) * | 2016-04-08 | 2016-06-15 | 河南顺达化工科技有限公司 | Technology for preparing ethanol from acetic ether through hydrogenation |
-
2017
- 2017-09-18 CN CN201710839160.9A patent/CN107573214A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155511A (en) * | 1996-01-22 | 1997-07-30 | 中国石化齐鲁石油化工公司 | Process and apparatus for converting methanol vapor into hydrogen |
| CN101965324A (en) * | 2008-02-28 | 2011-02-02 | 埃讷肯公司 | Production of ethanol from methanol |
| CN102766021A (en) * | 2012-07-24 | 2012-11-07 | 唐山市冀东溶剂有限公司 | Production system and production method for continuously producing ethanol by ethyl acetate through using hydrogenation |
| CN104555922A (en) * | 2015-01-23 | 2015-04-29 | 成都科特瑞兴科技有限公司 | New technology for producing hydrogen by conversion of methyl alcohol and water vapor |
| CN105669379A (en) * | 2016-04-08 | 2016-06-15 | 河南顺达化工科技有限公司 | Technology for preparing ethanol from acetic ether through hydrogenation |
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Application publication date: 20180112 |