CN220514123U - Coupling process system for ethanol dehydrogenation and byproduct hydrogenation - Google Patents

Coupling process system for ethanol dehydrogenation and byproduct hydrogenation Download PDF

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CN220514123U
CN220514123U CN202321445252.6U CN202321445252U CN220514123U CN 220514123 U CN220514123 U CN 220514123U CN 202321445252 U CN202321445252 U CN 202321445252U CN 220514123 U CN220514123 U CN 220514123U
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ethanol
hydrogen
gas
separation system
dehydrogenation
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景旭亮
李彦男
陈景
李鸿雄
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Shaanxi Yanchang Petroleum Group Co Ltd
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Shaanxi Yanchang Petroleum Group Co Ltd
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Abstract

The utility model discloses a coupling process system for ethanol dehydrogenation and byproduct hydrogenation, which comprises an ethanol preheating vaporization system and an ethanol dehydrogenation reaction system which are sequentially connected, wherein the ethanol dehydrogenation reaction system is also sequentially connected with a hydrogen separation system and an acetaldehyde separation system, and the acetaldehyde separation system is also connected with the hydrogen separation system through a first return pipeline; the coupling process system further comprises a compression system, a hydrogenation system and a gas-liquid separation system which are sequentially connected, wherein the gas-liquid separation system is respectively connected with an ethanol rectification system and the gas separation system; the acetaldehyde separation system is also connected with an ethanol rectification system, and the ethanol rectification system is also connected with an ethanol preheating and vaporizing system through a second return pipeline and a compression system through a third return pipeline; the compression system is connected with a hydrogen conveying pipeline, and the hydrogen separation system and the gas separation system are both connected with the hydrogen conveying pipeline. The utility model reduces the separation energy consumption of the ethanol dehydrogenation byproducts and realizes the high-efficiency utilization of the byproducts.

Description

Coupling process system for ethanol dehydrogenation and byproduct hydrogenation
Technical Field
The utility model belongs to the technical field of ethanol dehydrogenation, and particularly relates to a coupling process system for ethanol dehydrogenation and byproduct hydrogenation.
Background
At present, the industrial production routes of acetaldehyde in the world mainly comprise the following steps: ethylene oxidation, acetylene hydration, ethanol. Wherein the ethanol method is divided into an ethanol oxidation method and an ethanol catalytic dehydrogenation method; the ethanol catalytic dehydrogenation method is a synthetic route of synthesizing acetaldehyde by catalytic dehydrogenation of ethanol steam on a catalyst, and simultaneously, high-purity hydrogen is produced as a byproduct, so that the process is carried out in a fixed bed reactor, the production operation is simple, and the method has a great industrial application prospect in the synthesis of acetaldehyde.
Patent CN113680345a discloses a copper-containing heterogeneous catalyst, a preparation method and application thereof, wherein the application is ethanol dehydrogenation to acetaldehyde. However, there is a problem in the production system of the process in that the product includes hydrogen, ethyl acetate, butyraldehyde, butanol, etc., in addition to acetaldehyde. Among these products, hydrogen and acetaldehyde are light components, and can be easily separated from unreacted ethanol; the properties of ethyl acetate, butyraldehyde and ethanol are relatively close, and separation is difficult; however, since the butyraldehyde and ethyl acetate have a significant negative effect on the catalyst, the butyraldehyde and ethyl acetate must be removed. In the prior art, the technology for separating ethanol and ethyl acetate mainly comprises pressure swing rectification and the like, but the mass fraction of unreacted ethanol in other heavy components except acetaldehyde and diethyl ether in the product of preparing acetaldehyde by ethanol dehydrogenation is more than 95%, and the proportion of other trace impurities including ethyl acetate, butyraldehyde and butanol is very low, so even if pressure swing separation is adopted, the separation energy consumption is very high.
In addition, even if ethyl acetate and butyraldehyde are separated from ethanol in some way, the separation difficulty of ethyl acetate and butyraldehyde is high because the separation difficulty of ethyl acetate and butyraldehyde is high, and thus, ethyl acetate and butyraldehyde with high purity are required to be sold as products. At the same time, since the relative amounts of ethyl acetate and butyraldehyde are small, even if ethyl acetate and butyraldehyde are isolated in high purity, it is difficult to form a certain production scale, and sales are not optimistic.
For this reason, it is desirable to provide new process systems that are optimized for improvement over current process systems.
Disclosure of Invention
Aiming at the defects of the prior art, the utility model provides a coupling process system for ethanol dehydrogenation and byproduct hydrogenation, which is characterized in that a hydrogenation system is added to carry out hydrogenation treatment on byproducts of ethyl acetate and butyraldehyde to convert the byproducts into ethanol and butanol, so that the efficient conversion of byproducts of butyraldehyde and ethyl acetate is realized, and the byproducts of butyraldehyde and ethyl acetate are converted into ethanol and butanol; and the material separation and rectification process is simplified, and the energy consumption is reduced.
The coupling process system for ethanol dehydrogenation and byproduct hydrogenation comprises an ethanol preheating vaporization system and an ethanol dehydrogenation reaction system which are sequentially connected, wherein the ethanol dehydrogenation reaction system is also sequentially connected with a hydrogen separation system and an acetaldehyde separation system, and the acetaldehyde separation system is also connected with the hydrogen separation system through a first return pipeline;
the coupling process system further comprises a compression system, a hydrogenation system and a gas-liquid separation system which are sequentially connected, wherein the gas-liquid separation system is respectively connected with an ethanol rectification system and the gas separation system;
the acetaldehyde separation system is also connected with an ethanol rectification system, and the ethanol rectification system is also connected with an ethanol preheating and vaporizing system through a second return pipeline and a compression system through a third return pipeline;
the compression system is connected with a hydrogen conveying pipeline, and the hydrogen separation system and the gas separation system are both connected with the hydrogen conveying pipeline.
Preferably, the ethanol rectifying system is an ethanol rectifying tower, the second return pipeline is connected with the top of the ethanol rectifying tower, the connection ports of the acetaldehyde separating system, the gas-liquid separating system, the third return pipeline and the ethanol rectifying tower are positioned between the top and the bottom of the ethanol rectifying tower, and the connection ports of the gas-liquid separating system and the ethanol rectifying tower are positioned between the acetaldehyde separating system, the third return pipeline and the connection ports of the ethanol rectifying tower.
Preferably, the compression system comprises a gas booster and a liquid booster pump, the gas booster is connected with the hydrogen conveying pipeline, the liquid booster pump is connected with the third return pipeline, and the gas booster and the liquid booster pump are both connected with the hydrogenation system.
Preferably, the hydrogen separation system is an ethanol absorber.
Preferably, the hydrogen separation system further comprises a pre-pressurizing device connected with the ethanol absorption tower, and the pre-pressurizing device is connected with the ethanol dehydrogenation reaction system.
Preferably, the ethanol preheating and vaporizing system comprises a preheater and a vaporizer which are connected in sequence, and the vaporizer is connected with the ethanol dehydrogenation reactor.
Preferably, the gas separation system is a membrane separator or a pressure swing adsorption hydrogen plant.
The utility model has the advantages that:
the utility model reduces the separation energy consumption of the ethanol dehydrogenation byproducts and realizes the efficient utilization of the byproducts; separating hydrogen and acetaldehyde which are products of ethanol dehydrogenation by a hydrogen separation system and an acetaldehyde separation system, and carrying out hydrogenation treatment on byproducts of the dehydrogenation reaction by a hydrogenation system to enable ethyl acetate and butyraldehyde which are byproducts to be converted into ethanol and butanol which are easy to separate simply and efficiently; meanwhile, the byproduct hydrogen of ethanol dehydrogenation can be recycled in a hydrogenation system, and the supply and demand balance of the system hydrogen can be basically realized.
Drawings
FIG. 1 is a schematic diagram of a coupled process system for ethanol dehydrogenation and by-product hydrogenation;
wherein, 1-ethanol preheats vaporization system, 2-ethanol dehydrogenation reaction system, 3-hydrogen separation system, 4-acetaldehyde separation system, 5-compression system, 6-hydrogenation system, 7-gas-liquid separation system, 8-ethanol rectification system, 9-gas separation system, 10-first return line, 11-second return line, 12-third return line, 13-hydrogen delivery pipeline.
Detailed Description
The present utility model will be described in detail with reference to fig. 1.
The coupling process system for ethanol dehydrogenation and byproduct hydrogenation comprises an ethanol preheating vaporization system 1 and an ethanol dehydrogenation reaction system 2 which are sequentially connected, wherein the ethanol dehydrogenation reaction system 2 is also sequentially connected with a hydrogen separation system 3 and an acetaldehyde separation system 4, and the acetaldehyde separation system 4 is also connected with the hydrogen separation system 3 through a first return pipeline 10;
the coupling process system further comprises a compression system 5, a hydrogenation system 6 and a gas-liquid separation system 7 which are sequentially connected, wherein the gas-liquid separation system 7 is respectively connected with an ethanol rectifying system 8 and a gas separation system 9;
the acetaldehyde separation system 4 is also connected with the ethanol rectification system 8, and the ethanol rectification system 8 is also connected with the ethanol preheating and vaporizing system 1 through a second return pipeline 11 and the compression system 5 through a third return pipeline 12;
the compression system 5 is connected with a hydrogen conveying pipeline 13, and the hydrogen separation system 3 and the gas separation system 9 are both connected with the hydrogen conveying pipeline 13.
The ethanol rectifying system 8 is an ethanol rectifying tower, the second return pipeline 11 is connected with the top of the ethanol rectifying tower, connectors of the acetaldehyde separating system 4, the gas-liquid separating system 7 and the third return pipeline 12 and the ethanol rectifying tower are positioned between the top and the bottom of the ethanol rectifying tower, and connectors of the gas-liquid separating system 7 and the ethanol rectifying tower are positioned between the acetaldehyde separating system 4, the third return pipeline 12 and the connectors of the ethanol rectifying tower.
The compression system 5 comprises a gas booster connected to the hydrogen delivery conduit 13 and a liquid booster pump connected to the third return conduit 12, both of which are connected to the hydrogenation system 6.
The hydrogen separation system 3 is an ethanol absorption tower.
The hydrogen separation system 3 further comprises a pre-pressurizing device connected with the ethanol absorption tower, and the pre-pressurizing device is connected with the ethanol dehydrogenation reaction system 2.
The ethanol preheating and vaporizing system 1 comprises a preheater and a vaporizer which are sequentially connected, and the vaporizer is connected with an ethanol dehydrogenation reactor.
The gas separation system 9 is a membrane separator or a pressure swing adsorption hydrogen production device.
The working flow of the coupling process system for ethanol dehydrogenation and byproduct hydrogenation provided by the utility model is as follows:
the ethanol material enters an ethanol preheating and vaporizing system 1, is preheated to 80-150 ℃ in a preheater, and is further heated to 220-300 ℃ in the carburetor so as to meet the temperature requirement of dehydrogenation reaction, and a material WL2 is obtained;
feeding the material WL2 into alcohol dehydrogenation reaction system 2, and controlling alcohol mass space velocity at 220-300 deg.C and 0.05-0.5MPa for 2.0-10.0 hr -1 Dehydrogenation reaction is carried out under the condition, and the main product is hydrogen and ethyleneAldehyde, by-products mainly comprise ethyl acetate, butyraldehyde, butanol and other products, a material WL3 is obtained, and after cooling, the material WL3 enters a hydrogen separation system 3; the ethanol dehydrogenation reaction system 2 is realized by a fixed bed reactor, and the dehydrogenation catalyst is a catalyst ethanol dehydrogenation catalyst in the prior art, for example, a catalyst disclosed in patent CN113680345A can be adopted;
the hydrogen separation system 3 is an ethanol absorption tower, the reaction pressure of the ethanol absorption tower is consistent with the pressure of the ethanol dehydrogenation reaction system 2, the material WL3 enters the ethanol absorption tower, all substances except hydrogen are absorbed down, the substances are discharged from the ethanol absorption tower, the material WL4 is obtained, 99.9% of hydrogen in the material WL3 is separated, the material WL5 is obtained, and the material WL enters the hydrogen conveying pipeline 13; when the reaction pressure of the ethanol absorption tower is higher than the pressure of the ethanol dehydrogenation reaction system 2 and is 0.5-1.0MPa (but not 0.5), the hydrogen separation system 3 also comprises a pre-pressurizing device, and the material WL3 is pressurized by the pre-pressurizing device and then enters the ethanol absorption tower;
feeding the material WL4 into an acetaldehyde separation system 4, wherein the acetaldehyde separation system 4 is realized by an acetaldehyde rectifying tower, the pressure in the tower is controlled to be 0.3-1.0MPa, and the top product of the acetaldehyde rectifying tower is acetaldehyde with the purity of more than 99.7%; the other materials are taken as a tower bottom material WL7 and are divided into two paths, and one path of materials flows back to the hydrogen separation system 3 through the first return pipeline 10 to be taken as an absorbent; the other path of the liquid phase product material enters an ethanol rectifying system 8, ethanol in the liquid phase product material is rectified by an ethanol rectifying tower and enters an ethanol preheating and vaporizing system 1 through a second return pipeline 11 as circulating ethanol, and part of liquid phase product material 9-1 (mainly butyraldehyde, ethyl acetate and ethanol) enters a compression system 5 through a third return pipeline 12; the tower top of the acetaldehyde rectifying tower can use conventional cooling water as a cooling medium (instead of chilled water), so that the investment of a chilled water system is reduced;
in the compression system 5, the material 9-1 is pressurized by a liquid booster pump, hydrogen entering through a hydrogen conveying pipeline 13 is pressurized by a gas booster, the pressure of the pressurized gas and the pressure of the pressurized liquid are 3-8MPa, and the pressurized gas and the pressurized liquid enter the hydrogenation system 6;
the hydrogenation system 6 is realized by a fixed bed reactor, in whichIn the hydrogenation system 6, the raw materials are preheated to the reaction temperature of 220-600 ℃, and the mass airspeed of the liquid is 0.5-5h under the condition of 3-8MPa -1 Under the condition, respectively reacting hydrogen with ethyl acetate and hydrogen with butyraldehyde to generate ethanol and butanol; wherein, hydrogen: the molar ratio of (ethyl acetate and butyraldehyde) is 20-800:1, a step of; more preferably the molar ratio is 200-800:1, a step of; the catalyst used in the hydrogenation reaction is a supported catalyst, and the carrier is activated carbon or SiO 2 The active component loaded is one or more of Ru, re, pd, ag, ni, cu;
the products of the hydrogenation system 6 mainly comprise ethanol, butanol, unreacted hydrogen, trace amounts of unreacted butyraldehyde and ethyl acetate, and other trace amounts of light components such as ethane. The product enters a gas-liquid separation system 7 to divide the product into a gas phase and a liquid phase, wherein the gas phase component mainly comprises hydrogen, ethane and other trace light components, and the liquid phase component mainly comprises ethanol, butanol, trace unreacted butyraldehyde and ethyl acetate;
the gas phase component enters a gas separation system 9, when the gas separation system 9 is a membrane separator, permeation gas is hydrogen, and enters a hydrogen conveying pipeline 13 to circularly enter a gas booster in the compression system 5, and non-permeation gas is the other gas; when the gas separation system 9 is a pressure swing adsorption hydrogen production device, hydrogen penetrates through an adsorption bed layer, enters the compression system 5, enters the hydrogenation system 6 for recycling after being pressurized by a gas booster, light component gases such as ethane and the like on the other side are adsorbed, and then are collected after pressure equalization and desorption for a plurality of times, so that the hydrogen can be used as fuel gas;
the liquid phase component enters an ethanol rectifying system 8, is rectified by an ethanol rectifying tower, mainly obtains ethanol at the top of the tower, and enters an ethanol preheating and vaporizing system 1 through a second return pipeline 11 to be used as a raw material, and the tower bottom product mainly comprises butanol, trace ethyl acetate, butyraldehyde and other products; the pressure of the ethanol rectifying tower is controlled to be 1.5-3MPa, the molar reflux ratio of the top of the tower is 2-20, the butanol content obtained at the bottom of the tower is more than 95%, and the ethanol rectifying tower can be used as a crude product for external sales;
the hydrogen conveying pipeline 13 is a pipeline for conveying a hydrogen supplement stream or a product stream, and is specifically determined according to the process conditions of the hydrogenation unit; when the hydrogen consumption of the hydrogenation system 6 is low and the system is redundant, the redundant hydrogen is taken as a product to be sent out through the hydrogen conveying pipeline 13; when the hydrogen amount required by the hydrogenation system 6 is large and the system hydrogen amount is insufficient, a certain amount of hydrogen needs to be supplemented from the outside through the hydrogen conveying pipeline 13;
in the present utility model, the connection ports of the acetaldehyde separation system 4, the gas-liquid separation system 7, the third return line 12 and the ethanol rectification column are located between the top and the bottom of the ethanol rectification column, and the connection ports of the gas-liquid separation system 7 and the ethanol rectification column are located between the acetaldehyde separation system 4, the third return line 12 and the connection ports of the ethanol rectification column (for example, when the connection ports of the acetaldehyde separation system 4 and the ethanol rectification column are located at the 30 th tray, the connection ports of the gas-liquid separation system 7 and the ethanol rectification column are located at the 40 th tray, the bottom is located at the 60 th tray, the material 9-1 is extracted from the 50 th tray side line). Part of the material WL7 from the acetaldehyde rectifying tower is led into an ethanol rectifying system 8, and ethanol in the material WL7 is distilled and discharged from the top of the tower through rectification to be recycled as circulating ethanol; the bottom streams were butyraldehyde, ethyl acetate and butanol. The material 9-1 is extracted from the material flow at the position, because the content of ethanol in the material flow extracted at the position is greatly reduced, and meanwhile, the lowest content of butyraldehyde and ethyl acetate in the material flow at the bottom of the tower can be ensured, and the content of ethanol in each material flow gradually decreases from the top of the tower to the bottom of the tower.
Therefore, the coupling process system for ethanol dehydrogenation and byproduct hydrogenation provided by the utility model firstly removes light products (hydrogen and acetaldehyde) in the ethanol dehydrogenation products step by step through a hydrogen separation system and an acetaldehyde separation system to obtain heavy substances (ethanol, ethyl acetate, butyraldehyde and butanol); separating ethanol from heavy matters by an ethanol rectification system, pressurizing the separated ethanol and hydrogen, then introducing the mixture into a hydrogenation system, carrying out hydrogenation treatment on ethyl acetate and butyraldehyde in the mixture to convert the mixture into ethanol and butanol, carrying out gas-liquid separation on a hydrogenation reaction product, rectifying and separating a separated liquid phase to obtain heavy components mainly comprising butanol, and recycling the ethanol as a raw material for preparing acetaldehyde by ethanol dehydrogenation; separating the hydrogen in the light components after separation, and recycling the hydrogen to the hydrogenation unit for use; other light component gases include gases such as ethane generated by hydrogenation, and the like, and can be used as fuel gas to be produced outwards.
The whole process realizes the efficient conversion of byproducts butyraldehyde and ethyl acetate, and converts the byproducts butyraldehyde and ethyl acetate into ethanol and butanol; the material separation and rectification process is simplified, and the whole process has only one separation process of ethanol and heavy component butanol except a rectification tower of the product acetaldehyde, so that the energy consumption is low; finally, the hydrogen produced by ethanol dehydrogenation also realizes high-efficiency utilization.

Claims (7)

1. The coupling process system for ethanol dehydrogenation and byproduct hydrogenation comprises an ethanol preheating vaporization system (1) and an ethanol dehydrogenation reaction system (2) which are sequentially connected, and is characterized in that: the ethanol dehydrogenation reaction system (2) is also sequentially connected with a hydrogen separation system (3) and an acetaldehyde separation system (4), and the acetaldehyde separation system (4) is also connected with the hydrogen separation system (3) through a first return pipeline (10);
the coupling process system further comprises a compression system (5), a hydrogenation system (6) and a gas-liquid separation system (7) which are sequentially connected, wherein the gas-liquid separation system (7) is respectively connected with an ethanol rectification system (8) and a gas separation system (9);
the acetaldehyde separation system (4) is also connected with the ethanol rectification system (8), and the ethanol rectification system (8) is also connected with the ethanol preheating and vaporizing system (1) through a second return pipeline (11) and is connected with the compression system (5) through a third return pipeline (12);
the compression system (5) is connected with a hydrogen conveying pipeline (13), and the hydrogen separation system (3) and the gas separation system (9) are connected with the hydrogen conveying pipeline (13).
2. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 1, wherein: the ethanol rectifying system (8) is an ethanol rectifying tower, the second return pipeline (11) is connected with the top of the ethanol rectifying tower, the acetaldehyde separating system (4), the gas-liquid separating system (7), the third return pipeline (12) and the connecting ports of the ethanol rectifying tower are positioned between the top and the bottom of the ethanol rectifying tower, and the connecting ports of the gas-liquid separating system (7) and the ethanol rectifying tower are positioned between the acetaldehyde separating system (4), the third return pipeline (12) and the connecting ports of the ethanol rectifying tower.
3. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 2, wherein: the compression system (5) comprises a gas booster and a liquid booster pump, the gas booster is connected with the hydrogen conveying pipeline (13), the liquid booster pump is connected with the third return pipeline (12), and the gas booster and the liquid booster pump are both connected with the hydrogenation system (6).
4. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 3, wherein: the hydrogen separation system (3) is an ethanol absorption tower.
5. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 4, wherein: the hydrogen separation system (3) further comprises a pre-pressurizing device connected with the ethanol absorption tower, and the pre-pressurizing device is connected with the ethanol dehydrogenation reaction system (2).
6. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 5, wherein: the ethanol preheating and vaporizing system (1) comprises a preheater and a vaporizer which are sequentially connected, and the vaporizer is connected with an ethanol dehydrogenation reactor.
7. The coupled ethanol dehydrogenation and byproduct hydrogenation process system according to claim 6, wherein: the gas separation system (9) is a membrane separator or a pressure swing adsorption hydrogen production device.
CN202321445252.6U 2023-06-08 2023-06-08 Coupling process system for ethanol dehydrogenation and byproduct hydrogenation Active CN220514123U (en)

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