CN102942446A - Method for preparing ethanol via hydrogenation of acetic ester based on recirculating of recovered hydrogen - Google Patents
Method for preparing ethanol via hydrogenation of acetic ester based on recirculating of recovered hydrogen Download PDFInfo
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Abstract
The invention relates to a method for preparing ethanol via hydrogenation of acetic ester based on recirculating of recovered hydrogen. The method comprises the steps of: recycling hydrogen in the gas phase of a product by using a pressure swing adsorption (PSA) device and then increasing the pressure for recirculating; heating the mixed gas of acetic ester, circulated hydrogen and fresh hydrogen by using reaction heat; heating the preheated raw material gas by medium-pressure steam and then importing into a reactor so as to realize high acetic ester conversion rate and high ethanol selectivity in the presence of a catalyst; and carrying out gas-liquid separation on the product gas obtained via the reaction, and liquefying and separating the reaction principal product ethanol, a small amount of byproducts and unreacted acetic ester to obtain an initial product. According to the method, hydrogen is recycled and recirculated via PSA so that the use of the raw material hydrogen can be greatly reduced, the reaction raw materials are preheated by fully utilizing the reaction heat so that the energy consumption of the heating and the cooling is decreased, the flow is simple and the control is simple and convenient.
Description
Technical Field
The invention relates to a method for producing ethanol. In particular, the invention relates to a method for synthesizing ethanol by acetic ester gas phase hydrogenation by recycling hydrogen through pressure swing adsorption. Belongs to the technical field of chemical industry.
Background
Ethanol (CH)3CH2OH) is an important chemical raw material, and is widely used for producing and manufacturing paint, coating, printing ink, medicines, food and the like in the fields of chemical industry and other industries; meanwhile, ethanol is an important clean energy source, has high oxygen content, high vaporization latent heat and good anti-explosion performance, has the excellent characteristics of more complete combustion, lower CO emission and the like when being used as vehicle fuel, and has been popularized and approved worldwide.
The national condition that the energy distribution in China is 'lean oil and rich coal' and the petroleum resources are relatively deficient restricts the development of the process route for synthesizing the ethanol by taking the petroleum as the raw material. The coal price is relatively cheap compared to the oil price at a high level. In recent years, the scale of domestic coal chemical industry is rapidly enlarged, so that the price of the acetic acid product in the coal chemical industry is continuously reduced. Therefore, the development of the process technology for preparing the ethanol by hydrogenation of the acetic ester by taking the coal as the raw material can fully exert the advantage of rich coal resources in China.
The reported process for preparing ethanol by catalytic hydrogenation by taking acetate as a raw material adopts more Cu-series catalysts at present, the conversion rate of the acetate in the reaction can reach more than 95 percent, and the selectivity of the ethanol can reach more than 97 percent. In order to effectively inhibit side reactions, hydrogen needs to be greatly excessive in the reaction, and the molar ratio of the hydrogen to the acetic ester is generally 20-100: 1. In the conventional production process, a large amount of unreacted hydrogen (containing a small amount of inert components and byproducts) circulates in a circulation loop of a reaction system, so that in order to ensure that the inert components and the hydrogenation byproducts are accumulated in the circulating gas to influence the hydrogenation reaction effect, the circulating gas needs to be partially discharged. The fresh hydrogen addition amount caused by the purge is obviously higher than the fresh hydrogen amount required by the hydrogenation reaction, so that a great deal of waste of hydrogen is caused. Meanwhile, the reaction product is cooled to normal temperature at least to condense and separate the condensable components, and then the separated low-temperature circulating hydrogen, fresh hydrogen and circulating hydrogen are reheated and enter the reactor, so that a large amount of heat is consumed, and huge economic loss is caused.
Disclosure of Invention
The invention aims to provide a novel method for preparing ethanol by hydrogenating acetic ester, which optimizes the reaction flow, saves hydrogen as a raw material to a greater extent, and saves cooling water and steam for heating at the same time, thereby saving raw materials and energy and reducing the cost.
In one aspect, the present invention provides a method for continuously preparing ethanol by catalytic hydrogenation of acetic ester, comprising the steps of:
i) preheating fresh hydrogen 2 to obtain high-temperature hydrogen 5 with the temperature of 170-240 ℃;
ii) preheating the acetate 1 to obtain preheated acetate 3 with the temperature of 190 ℃ and 250 ℃;
iii) mixing the high-temperature hydrogen 5 obtained in the step i) with the preheated acetate 3 obtained in the step ii), gasifying the mixture by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-290 ℃, and heating the mixture to 230-290 ℃;
iv) separating the substance obtained in the step iii) to obtain a raw material gas 8 with the temperature of 230-290 ℃ and acetic ester 7 which is not completely gasified, and carrying out hydrogenation reaction on the raw material gas 8 to obtain a high-temperature product gas 9 with the temperature of 250-310 ℃; respectively exchanging heat between the high-temperature product gas 9 and acetic ester 1 and fresh hydrogen 2 to obtain a cooled product gas 11 with the temperature of 60-90 ℃; cooling the cooled product gas 11 to obtain a gas-liquid two-phase product gas-liquid 12 with the temperature of 30-40 ℃; carrying out gas-liquid separation on the gas-liquid two-phase product gas-liquid 12 to obtain a primary product 13 and a circulating gas 14; removing organic components from the recycle gas 14 through pressure swing adsorption to obtain a pressure swing adsorbed resolution matter 17 and a pressure swing adsorbed product gas 15, and boosting the pressure of the pressure swing adsorbed product gas 15 to obtain recycle hydrogen 16 which is used as fresh hydrogen 2 to return to the system for reaction; and
v) separating the desorbed analyzed product 17 and the primary product 13 together to obtain an ethanol product 18 and a vent gas 19.
Preferably, the method further comprises the following step vi): returning the incompletely gasified acetic ester 7 obtained in the step iv) to the step iii), mixing with the preheated acetic ester 3 and the high-temperature hydrogen 5, gasifying by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-290 ℃, and heating to 230-290 ℃.
Preferably, the purity of the recycled hydrogen 16 obtained in step iv) is 95 mol% or more, more preferably 96 mol% or more.
Preferably, the temperature of the high-temperature hydrogen 5 is 170-235 ℃, more preferably 200-230 ℃.
Preferably, the acetate 1 is selected from one or more of methyl acetate and ethyl acetate, and more preferably is ethyl acetate.
Preferably, the temperature of the preheated acetate 3 is 220-240 ℃.
Preferably, the temperature of the feed gas 8 is 250-270 ℃.
In another aspect, the present invention also provides an apparatus for continuously preparing ethanol by catalytic hydrogenation of acetic ester, the apparatus comprising:
gas- liquid separators 23, 26, 31 for separating gas and liquid phases;
a hydrogenation reactor 24 connected to the gas-liquid separator 23 for converting the raw gas 8 into a high-temperature product gas 9;
a pressure swing adsorption unit 27 connected to the gas-liquid separator 26 for removing organic components from the recycle gas;
a recycle compressor 28 connected between the pressure swing adsorption device 27 and the hydrogen preheater 21 for increasing the pressure of the recycle gas from which the organic components are removed to obtain recycle hydrogen 16;
and the vaporizer 22 is connected to the hydrogen preheaters 20 and 21 and the gas-liquid separator 23, and is configured to vaporize the preheated acetic esters 3, the high-temperature hydrogen 5, and the incompletely vaporized acetic esters 7.
Preferably, the plant further comprises a temperature control valve 30, and the temperature of the raw gas 8 entering the hydrogenation reactor 24 is controlled by controlling the amount of medium pressure steam in the gasifier 22 through the temperature control valve 30.
Preferably, the gasifier 22 also serves to provide for adequate gas-liquid phase contact and reduced gas phase drag.
The invention can be realized by the following embodiments:
a) mixing fresh hydrogen 2 with circulating hydrogen 16 finally obtained by the process, and then carrying out heat exchange in a heat exchanger (also called a hydrogen preheater) 21 to obtain high-temperature hydrogen 5, wherein the temperature is 170-;
b) heat exchanging the acetic ester 1 in a heat exchanger (also called an acetic ester preheater) 20 to obtain preheated acetic ester 3 at the temperature of 190 ℃ and 250 ℃;
c) mixing high-temperature hydrogen 5 and preheated acetic ester 3, gasifying by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-500 ℃, and heating to 230-290 ℃;
d) separating the substance obtained in the step c) to obtain raw material gas 8 with the temperature of 230-290 ℃ and incompletely gasified acetic ester 7; feeding the separated feed gas 8 with the temperature of 230-290 ℃ into a hydrogenation reactor 24 for hydrogenation reaction to obtain a high-temperature product gas 9 with the temperature of 250-310 ℃; respectively exchanging heat of the high-temperature product gas 9 with acetic ester 1 and fresh hydrogen 2 through heat exchangers 20 and 21 to obtain a cooled product gas 11 with the temperature of 60-90 ℃; the cooled product gas 11 is cooled to 30-40 ℃ by circulating water in a heat exchanger (also called a circulating water heat exchanger) 25 to obtain a gas-liquid two-phase product gas-liquid 12; then, gas-liquid separation is carried out on the gas-liquid 12 of the gas-liquid two-phase product in a gas-liquid separator 26 to obtain a primary product 13 and a circulating gas 14; removing organic components in the recycle gas 14 by a Pressure Swing Adsorption (PSA) device 27, boosting the pressure by a recycle compressor 28 to obtain recycle hydrogen 16, and returning the recycle hydrogen 16 as fresh hydrogen 2 to the system for reaction; at this time, the mixture of the circulating hydrogen 16 and the fresh hydrogen 2 is mixed hydrogen 4;
e) the desorption product 17 of Pressure Swing Adsorption (PSA) and the primary product 13 enter a gas-liquid separator 31 of low-pressure products together, and ethanol products 18 and vent gas 19 are obtained after separation.
In an optional embodiment, the above embodiment further comprises step f): returning the incompletely gasified acetic ester 7 to the step c), mixing with the preheated acetic ester 3 and the high-temperature hydrogen 5, gasifying by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-500 ℃, heating to 230-290 ℃, circulating in such a way, and finally separating a little acetic ester which is not gasified by using a gas-liquid separator 23;
in the above embodiments, the acetate is selected from one or more of methyl acetate and ethyl acetate; preferably, the acetate is ethyl acetate.
In the above embodiment, in the step a), the temperature of the high-temperature hydrogen 5 is 170-; in the step c), the temperature of the raw material gas entering the hydrogenation reactor is controlled by controlling the medium-pressure steam quantity of the vaporizer, and the vaporizer is gas-liquid mass transfer equipment which can ensure full contact of gas and liquid phases and small gas-phase resistance; in the step b), the temperature of the preheated acetate 3 is 190-250 ℃, preferably, the temperature is 220-240 ℃; in the step d), the temperature of the feed gas 8 is 230-290 ℃, preferably 250-270 ℃; in the step d), the recycle gas 14 is subjected to organic removal by using PSA to obtain recycle hydrogen 16 with higher hydrogen purity, and the recycle hydrogen is used as fresh hydrogen 2 to return to the system for reaction.
Compared with the prior art, the method for continuously preparing the ethanol by acetate hydrogenation adopts a Pressure Swing Adsorption (PSA) device to recover hydrogen in a product gas phase, then the pressure is increased for circulation, the mixed gas of the acetate, the circulating hydrogen and the fresh hydrogen is heated by reaction heat, the preheated feed gas enters a reactor after being heated by medium-pressure steam, and the high acetate conversion rate and the high ethanol selectivity are realized under the action of a catalyst. And carrying out gas-liquid separation on the product gas obtained by the reaction, and then liquefying and separating the main reaction product ethanol, a small amount of by-products and unreacted acetic ester to obtain a primary product. The method can greatly reduce the use of the raw material hydrogen by recycling the hydrogen recovered by PSA, fully utilizes the reaction heat to preheat the reaction raw material and reduce the energy consumption of heating and cooling, and has simple process and simple and convenient control. In short, the method optimizes the hydrogen circulation flow and saves the raw material hydrogen to a greater extent; the heat exchange network is optimized to save cooling water and steam for heating, thereby saving raw materials and energy and reducing cost.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a process flow diagram of a process according to the invention; wherein,
1-acetate; 2-fresh hydrogen; 3-acetic ester after preheating; 4-mixed hydrogen; 5-high temperature hydrogen; 6-acetic ester after gasification; 7-incompletely vaporized acetate; 8-raw material gas; 9-high temperature product gas; 10-cooling the product gas; 11-cooled product gas; 12-gas-liquid two-phase product gas-liquid; 13-primary product; 14-circulating gas; 15-pressure swing adsorption of product gas; 16-recycle hydrogen; 17-PSA analyte; an 18-ethanol product; 19-venting air; 20-heat exchanger (acetate preheater); 21-heat exchanger (hydrogen preheater); 22-a gasifier; 23. 26, 31-gas-liquid separator; 24-a hydrogenation reactor; 25-heat exchanger (circulating water heat exchanger); 27-a pressure swing adsorption unit; 28-a recycle compressor; 29-temperature sensor and 30-temperature control valve, the unmarked lines are pipelines.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
Examples
The following describes an embodiment with reference to fig. 1. 3.5L of hydrogenation Cu catalyst is loaded in the middle of the hydrogenation reactor 24, ceramic rings with the same particle size as the catalyst are arranged at two ends of the reactor, ethyl acetate is used as a raw material, and the reaction pressure of the hydrogenation reaction is 2.5MPa (gauge pressure).
The high temperature hydrogen 5, preheated acetate 3 and, optionally, incompletely vaporized acetate 7 (indicated by a dotted line) are mixed in a vaporizer 22 and vaporized by medium pressure steam at a pressure of 3-5MPa and a temperature of 300-500 ℃ and heated to 250 ℃. After heat exchange, most of the acetic ester is gasified and discharged from the top of the gas-liquid separator 23 with the hydrogen to enter the next process, and the gas-liquid separator 23 returns a very small amount of incompletely gasified acetic ester 7 to the bottom of the gasifier 22 for cyclic gasification operation. Meanwhile, the method controls the opening degree of a temperature control valve 30 by sensing the temperature through a temperature sensor 29 so as to control the medium-pressure steam amount and control the temperature of the raw material gas 8 at the inlet of the hydrogenation reactor 24, wherein the temperature is controlled to be 250 ℃, and the mole fraction of hydrogen is 96.6%, the mole fraction of acetate is 1.4%, and the mole fraction of other components such as nitrogen is 2.0%. The raw material gas 8 enters a hydrogenation reactor 24 to contact and react with a Cu catalyst to obtain high-temperature product gas 9. The conversion rate of the acetic ester is analyzed to be 98.5%, and the components in the high-temperature product gas 9 at the outlet of the hydrogenation reactor 24 are calculated according to the mole fraction: 95.1 percent of hydrogen, 0.3 percent of acetic ester, 2.6 percent of ethanol, 2.0 percent of water, nitrogen and other components. Since the reaction is exothermic, the temperature of the high temperature product gas 9 rises to 270 ℃ at the outlet of the hydrogenation reactor 24. The high-temperature product gas 9 and the acetic ester 1 are cooled to 242 ℃ after heat exchange in the hydrogen preheater 20, and the cooled product gas 10 enters the hydrogen preheater 21 to be cooled to 82 ℃ after heat exchange with the mixed hydrogen 4, so that the cooled product gas 11 is obtained. The cooled product gas 11 is cooled to 40 ℃ by circulating water in a circulating water heat exchanger 25 to obtain a gas-liquid two-phase product gas-liquid 12.
The gas-liquid two-phase product gas-liquid 12 enters a product gas-liquid separator 26 for gas-liquid separation to obtain a circulating gas 14 and an initial product 13. The outlet temperature of the top gas (recycle gas 14) of the product gas-liquid separator 26 is 40 ℃, wherein the gas comprises the following components in mole fraction: 96.9% of hydrogen, 0.1% of acetic ester, 0.8% of ethanol, 2.1% of water, nitrogen and other components; the temperature of the bottom liquid phase initial product 13 is 40 ℃, wherein the liquid phase initial product 13 comprises the following components in molar fraction: 0.2 percent of hydrogen, 0.6 percent of acetic ester, 94.7 percent of ethanol, 4.4 percent of water, nitrogen and other components. Separating the initial product 13 by using a gas-liquid separator 31 of a low-pressure product to obtain a product 18, wherein the temperature of the product is 40 ℃, and the components in the product 18 comprise the following components in molar fraction: 0.06% of hydrogen, 0.6% of acetic ester, 95.2% of ethanol, 4.2% of water, nitrogen and other components.
The recycle gas 14 is subjected to a Pressure Swing Adsorption (PSA) unit 27 to remove organic substances therein, so as to obtain relatively pure hydrogen (i.e., a pressure swing adsorbed product gas 15), which comprises the following components in terms of mole fraction: 99.8 percent of hydrogen, 0.2 percent of nitrogen and other components. The pressure of the recycle gas is increased by a recycle compressor 28 to obtain recycle hydrogen 16 which is returned to the system for reaction.
According to the analysis results, the average conversion rate of acetic ester is 98.5%, and the average selectivity of ethanol is 98.8%.
In the prior art, a large amount of unreacted hydrogen (containing a small amount of inert components and byproducts) circulates in a circulation loop of a reaction system, so that in order to ensure that the inert components and the hydrogenation byproducts are accumulated in the circulation gas to influence the hydrogenation reaction effect, the circulation gas needs to be partially exhausted, and the volume ratio of the exhaustion to the circulation is generally 0.08-0.1. However, based on the amount of feed in this example, the prior art using purge mode needs to make up fresh hydrogen amount of 2m3The invention only needs to supplement fresh hydrogen with the amount of 0.75m by adopting the mode of PSA recycling hydrogen3And/h, the fresh hydrogen amount can be saved by about 60 percent by adopting the process through calculation.
Likewise, ethanol production by prior art processes requires heating of the recycle hydrogen and acetate,at the same time, the reaction product must be cooled. In this process, the heat load Q =3.5Kw for heating the recycle hydrogen and acetate or cooling the reaction product, and the required 3.4MPa (absolute) superheated steam (temperature 430 ℃ C.) is about 5kgh-1Or 137kgh-1. Based on the product amount, a steam amount of about 2kg/kg product or a circulating water amount of about 40kg/kg product is required, here according to example 2.65kgh of the present invention-1Is calculated from the capacity of the raw material feed (corresponding to a pilot scale of 20 tons of ethanol produced annually). However, the method of the present invention does not require the heating and cooling steps in the above calculation, and therefore can save the amount of steam and the amount of circulating water equal to the amount of heating and cooling steam and the amount of circulating water calculated above.
Claims (10)
1. A process for the continuous production of ethanol by the catalytic hydrogenation of acetate, said process comprising the steps of:
i) preheating fresh hydrogen (2) to obtain high-temperature hydrogen (5) with the temperature of 170-240 ℃;
ii) preheating the acetate (1) to obtain preheated acetate (3) with the temperature of 190 ℃ and 250 ℃;
iii) mixing the high-temperature hydrogen (5) obtained in the step i) with the preheated acetate (3) obtained in the step ii), gasifying the mixture by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-500 ℃, and heating the mixture to 230-290 ℃;
iv) separating the substance obtained in the step iii) to obtain a raw material gas (8) with the temperature of 230-290 ℃ and acetic ester (7) which is not completely gasified, and carrying out hydrogenation reaction on the raw material gas (8) to obtain a high-temperature product gas (9) with the temperature of 250-310 ℃; respectively exchanging heat between the high-temperature product gas (9) and acetic ester (1) and fresh hydrogen (2) to obtain a cooled product gas (11) with the temperature of 60-90 ℃; cooling the cooled product gas (11) to obtain a gas-liquid two-phase product gas-liquid (12) with the temperature of 30-40 ℃; carrying out gas-liquid separation on the gas-liquid two-phase product gas-liquid (12) to obtain a primary product (13) and a circulating gas (14); removing organic components in the recycle gas (14) through pressure swing adsorption to obtain a pressure swing adsorption resolution substance (17) and a pressure swing adsorption product gas (15), and boosting the pressure of the pressure swing adsorption product gas (15) to obtain recycle hydrogen (16) which is used as fresh hydrogen (2) to return to the system for reaction; and
v) separating the pressure swing adsorption analysis product (17) and the primary product (13) together to obtain an ethanol product (18) and a vent gas (19).
2. The method according to claim 1, wherein the method further comprises the following step vi): returning the incompletely gasified acetic ester (7) obtained in the step iv) to the step iii), mixing with the preheated acetic ester (3) and the high-temperature hydrogen (5), gasifying by medium-pressure steam with the pressure of 3-5MPa and the temperature of 300-500 ℃, and heating to 230-290 ℃.
3. The process according to claim 1, wherein the purity of the recycled hydrogen (16) obtained in step iv) is 95 mol% or more, preferably 96 mol% or more.
4. The process according to claim 1 or 2, wherein the temperature of the high temperature hydrogen (5) is 170-.
5. A process according to any one of claims 1 to 3, wherein the acetate (1) is selected from one or more of methyl acetate and ethyl acetate, and is preferably ethyl acetate.
6. The process according to any one of claims 1 to 5, wherein the temperature of the pre-heated acetate (3) is 220-240 ℃.
7. The process as claimed in any of claims 1 to 5, wherein the temperature of the feed gas (8) is 250-270 ℃.
8. An apparatus for the continuous production of ethanol by the catalytic hydrogenation of acetate, the apparatus comprising:
a gas-liquid separator (23, 26, 31) for separating a gas phase and a liquid phase;
a hydrogen preheater (20, 21, 25) for exchanging heat;
a hydrogenation reactor (24) connected to the gas-liquid separator (23) for converting the feed gas (8) into a high temperature product gas (9);
a pressure swing adsorption unit (27) connected to the gas-liquid separator (26) for removing organic components from the recycle gas;
a recycle compressor (28) connected between the pressure swing adsorption device (27) and the hydrogen preheater (21) and used for boosting the recycle gas without organic components to obtain recycle hydrogen (16);
and the gasifier (22) is respectively connected with the hydrogen preheaters (20 and 21) and the gas-liquid separator (23) and is used for gasifying the preheated acetic ester (3), the high-temperature hydrogen (5) and the incompletely gasified acetic ester (7).
9. The plant according to claim 8, wherein the plant further comprises a thermo valve (30), by means of which thermo valve (30) the medium pressure steam amount of the gasifier (22) is controlled to control the temperature of the feed gas (8) entering the hydrogenation reactor (24).
10. Apparatus according to claim 8 or 9, wherein said gasifier (22) is further adapted to bring the gas-liquid phase into full contact and to reduce gas phase drag.
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| CN103588619A (en) * | 2013-11-20 | 2014-02-19 | 天津大学 | Production method and device for producing ethanol from methyl acetate by adding hydrogen |
| CN103588619B (en) * | 2013-11-20 | 2016-08-17 | 天津大学 | The production method of methyl acetate preparation of ethanol by hydrogenating and device |
| CN105439816A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A process of producing ethanol by acetate hydrogenation |
| 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 |
| CN105523880A (en) * | 2014-09-29 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Method for preparing ethylene from acetate |
| CN105523880B (en) * | 2014-09-29 | 2018-01-26 | 大唐国际化工技术研究院有限公司 | A kind of method by acetate ethene |
| CN105523887A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Method for high selectivity preparation of alcohol from ester |
| CN105585421A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | High-selectivity method for preparing alcohol from ester |
| CN105523887B (en) * | 2014-10-24 | 2018-07-17 | 中国石油化工股份有限公司 | The highly selective method for preparing alcohol of ester |
| CN105585421B (en) * | 2014-10-24 | 2018-01-09 | 中国石油化工股份有限公司 | The method that ester high selectivity prepares alcohol |
| CN104860796A (en) * | 2015-05-04 | 2015-08-26 | 河南顺达化工科技有限公司 | Heat exchange unit ethanol synthesis process |
| CN104860796B (en) * | 2015-05-04 | 2018-03-02 | 河南顺达化工科技有限公司 | A kind of technique with heat-exchange unit synthesizing alcohol |
| CN105669379B (en) * | 2016-04-08 | 2018-02-23 | 河南顺达化工科技有限公司 | A kind of technique of ethyl acetate preparation of ethanol through hydrogenation |
| 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 |
| CN106008155A (en) * | 2016-06-22 | 2016-10-12 | 江苏索普（集团）有限公司 | Integrated device and method for preparing ethanol from acetic acid and ethyl acetate through hydrogenation reaction |
| CN109422623A (en) * | 2017-08-20 | 2019-03-05 | 杭州林达化工技术工程有限公司 | A kind of energy-saving acetic acid adds the production technology and its device of hydrogen or ethyl acetate preparation of ethanol by hydrogenating |
| CN113461485A (en) * | 2021-06-18 | 2021-10-01 | 国家能源投资集团有限责任公司 | System and method for preparing crude ethanol by hydrogenation of hydrogenation raw material and application |
| CN113461485B (en) * | 2021-06-18 | 2023-08-22 | 国家能源投资集团有限责任公司 | System, method and application for preparing crude ethanol by hydrogenation of hydrogenation raw material |
| CN119406075A (en) * | 2025-01-06 | 2025-02-11 | 北京弗莱明科技有限公司 | Product separation device and method for preparing ethanol by hydrogenation of energy-saving acetate |
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