阅读说明：本技术 一种高温电化学装置辅助制备合成气的装置和方法 (Device and method for preparing synthesis gas with assistance of high-temperature electrochemical device ) 是由 王建强 程付鹏 关成志 陆越 万松 于 2020-07-24 设计创作，主要内容包括：本发明涉及一种高温电化学装置辅助制备合成气的装置,包括从工业废气中分离出水蒸气后得到剩余气体的脱水处理装置；电解水蒸气得到氢气和氧气的SOEC系统；将剩余气体和天然气进行脱硫处理分别得到高纯CO<Sub>2</Sub>气体和高纯CH<Sub>4</Sub>气体的脱硫处理装置；双重整系统包括利用高纯CO<Sub>2</Sub>气体和氢气进行逆水煤气变换反应制备合成气的第一反应室和利用高纯CH<Sub>4</Sub>气体和氧气进行部分氧化反应制备合成气的第二反应室。本发明还涉及一种高温电化学装置辅助制备合成气的方法。根据本发明的高温电化学装置辅助制备合成气的装置,通过SOEC系统和双重整系统的耦合,可以利用工业废气和天然气来制备不同比例的合成气。(The invention relates to a device for preparing synthesis gas with the assistance of a high-temperature electrochemical device, which comprises a dehydration treatment device for separating water vapor from industrial waste gas to obtain residual gas; an SOEC system for electrolyzing water vapor to obtain hydrogen and oxygen; respectively carrying out desulfurization treatment on the residual gas and the natural gas to obtain high-purity CO 2 Gas and high purity CH 4 A gas desulfurization treatment device; the dual reforming system includes the utilization of high purity CO 2 First reaction chamber for preparing synthetic gas by gas and hydrogen gas inverse water gas shift reaction and method for preparing synthetic gas by using high-purity CH 4 Partial oxidation of gas and oxygenAnd a second reaction chamber for preparing synthesis gas by chemical reaction. The invention also relates to a method for preparing the synthesis gas by the aid of the high-temperature electrochemical device. According to the device for preparing the synthesis gas by the aid of the high-temperature electrochemical device, the synthesis gas with different proportions can be prepared by utilizing industrial waste gas and natural gas through the coupling of the SOEC system and the double reforming system.)

1. A device for preparing synthesis gas with the assistance of a high-temperature electrochemical device is characterized by comprising:

a dehydration treatment device which is communicated with the industrial waste gas to obtain residual gas after water vapor is separated from the industrial waste gas;

the SOEC system is communicated with the dehydration treatment device to electrolyze water vapor to obtain hydrogen and oxygen in the SOEC system;

a first desulfurization treatment device communicated with the residual gas to perform desulfurization treatment on the residual gas to obtain high-purity CO₂A gas;

second desulfurization treatment device, it and natural gasCommunicated with natural gas to be desulfurized to obtain high-purity CH₄A gas;

a double reforming system connected downstream of the SOEC system, comprising a first reaction chamber and a second reaction chamber, wherein the first reaction chamber is respectively connected with a first desulfurization treatment device and the SOEC system to utilize high purity CO₂The gas and hydrogen are subjected to inverse water-gas shift reaction to prepare synthesis gas, and the second reaction chamber is respectively connected with a second desulfurization treatment device and an SOEC system to utilize high-purity CH₄The gas and oxygen are subjected to partial oxidation reaction to prepare synthesis gas.

2. The apparatus of claim 1, wherein the hydrogen and the vapor mixture of the SOEC system are separated at high temperature by a metal Pd membrane separator to obtain hydrogen.

3. The apparatus of claim 1, wherein the first desulfurization treatment apparatus is connected downstream of the SOEC system to perform hydrodesulfurization of the residual gas using a portion of hydrogen obtained from the SOEC system, wherein the portion of hydrogen obtained from the SOEC system is reacted with sulfur-containing compounds in the residual gas as a desulfurization-treated raw material to complete desulfurization.

4. The apparatus of claim 1, wherein the second desulfurization treatment unit is connected downstream of the SOEC system to perform hydrodesulfurization of the natural gas using another portion of the hydrogen from the SOEC system, wherein the another portion of the hydrogen from the SOEC system is used as a desulfurization-treated feedstock to react with sulfur-containing compounds in the natural gas to complete desulfurization.

5. The apparatus of claim 1, wherein the high purity CO is₂Gas and/or high purity CH₄The sulfur content of the gas was below 0.1ppm each.

6. The apparatus of claim 1, further comprising a gas separation system connected downstream of the dual reforming system, wherein the mixed gas from the first reaction chamber and the second reaction chamber enters the gas separation system to separate the syngas.

7. The apparatus of claim 6, wherein the gas separation system comprises a low pressure storage tank, a booster pump, and a pressure swing adsorption gas separation unit, wherein the low pressure storage tank is in communication with the first reaction chamber and the second reaction chamber for storing the syngas, unreacted CO, produced by the first reaction chamber and the second reaction chamber₂A booster pump for boosting is arranged between the low-pressure storage tank and the pressure swing adsorption gas separation device to convey the boosted mixed gas to the pressure swing adsorption gas separation device, the pressure swing adsorption gas separation device for separating the mixed gas is communicated with the first reaction chamber and the second reaction chamber, and the separated unreacted CO is₂The gas is returned to the first reaction chamber and the separated unreacted natural gas is returned to the second reaction chamber.

8. The apparatus of claim 1, further comprising a thermal management system coupled to the SOEC system and the first reaction chamber to provide thermal energy, and coupled to the second reaction chamber to recover the thermal energy.

9. A method for preparing synthesis gas with the assistance of a high-temperature electrochemical device is characterized by comprising the following steps:

separating water vapor from the industrial waste gas by a dehydration treatment device to obtain residual gas;

electrolyzing the water vapor through a SOEC system to obtain hydrogen and oxygen;

the residual gas is desulfurized by a first desulfurization treatment device to obtain high-purity CO₂A gas;

the natural gas is desulfurized by a second desulfurization treatment device to obtain high-purity CH₄A gas;

high purity CO₂Gas and hydrogen are subjected to inverse water gas shift reaction in a first reaction chamber of the double-integrated system to prepare synthesis gas, high-purity CH₄Gas and oxygen in the second reaction chamber of the double integrated systemThe partial oxidation reaction is carried out to prepare the synthesis gas.

10. The method of claim 9, wherein the flow rate of water vapor into the SOEC system is from 0.1MpaG to 5.0 MpaG.

11. The method according to claim 9, wherein the flow molar ratio of the residual gas entering the first desulfurization treatment device to the hydrogen entering the first desulfurization treatment device is 1:1 to 20: 1.

12. The method of claim 9, wherein the flow molar ratio of the natural gas entering the second desulfurization treatment device to the hydrogen entering the second desulfurization treatment device is 6:1 to 20: 1.

13. The method of claim 9, wherein the high purity CO entering the first reaction chamber₂The molar ratio of the flow rate of the gas to the flow rate of the hydrogen entering the first reaction chamber is 0.1:1-3: 1.

14. The method of claim 9, wherein the high purity CH entering the second reaction chamber₄The molar ratio of the flow rate of the gas to the flow rate of the oxygen entering the second reaction chamber is 0.1:1-3: 1.

15. The method of claim 9, wherein the mixed gas from the first reaction chamber and the second reaction chamber is fed into a gas separation system to separate the syngas from the unreacted CO₂Separating gas and unreacted natural gas, and subjecting the synthetic gas to pressure swing separation to obtain H₂The ratio/CO is in the range of 1 to 5.

16. The method of claim 9, wherein the SOEC system is operated at a temperature of 550 ℃ to 850 ℃.

Technical Field

The invention relates to combined utilization of industrial waste gas and natural gas, in particular to a device and a method for preparing synthesis gas by assistance of a high-temperature electrochemical device.

Background

At present, with the increasing severity of greenhouse effect, human beings pay attention to global warming and climate change caused by energy consumption, and the use of a large amount of fossil fuels and excessive emission of industrial waste gas into the atmosphere are the main causes of energy consumption and greenhouse effect. The waste heat of industrial waste gas contains a large amount of CO₂And steam, with a large amount of industrial waste heat. Natural gas contains a large amount of CH₄。CO₂And CH₄As a major component of greenhouse gases, the emission of these carbon-containing gases into the atmosphere is a major factor that exacerbates the global warming effect. CO in industrial waste gas₂The conversion of the gas into the synthesis gas which can be reused to realize the capture of the carbon source and the reduction of the emission of greenhouse gases into the atmosphere is one of the effective ways to reduce the energy consumption and relieve the global warming effect.

A Solid Oxide Electrolytic Cell (SOEC) is a device that generates fuel gas (chemical energy) by electrochemically reducing raw materials such as water and carbon dioxide using electric energy and thermal energy, and is considered to be one of the most promising energy conversion devices. The water is the main raw material for preparing the hydrogen by electrolyzing the water at high temperature, and has the characteristics of convenient material acquisition, rich raw materials, multiple recycling property and the like. When the high-temperature solid oxide electrolytic cell operates, water vapor is decomposed to generate hydrogen at the cathode of the SOEC, oxygen ions are conducted to the anode through the electrolyte membrane, and oxygen is generated on the surface of the anode material. CN20171031531.4 discloses CO-electrolysis of CO by using solid oxidation electrolytic cell₂/H₂O method for preparing synthetic gas by introducing CO into negative electrode₂It will cause problems of carbon deposition on the negative electrode, which will greatly reduce the performance of the electrolytic cell andand (4) durability. Introducing CO₂And H₂The method for preparing the synthesis gas by co-electrolysis of O blindly ignores the practical application condition of the SOEC galvanic pile, so that the service life of the SOEC galvanic pile is sharply reduced and the method is difficult to realize in industrial application.

Disclosure of Invention

In order to solve the problems of carbon deposition of a negative electrode and the like in the prior art, the invention provides a device and a method for preparing synthesis gas by using a high-temperature electrochemical device in an auxiliary manner.

According to the present invention, there is provided an apparatus for auxiliary preparation of synthesis gas for a high temperature electrochemical device, comprising: a dehydration treatment device which is communicated with the industrial waste gas to obtain residual gas after water vapor is separated from the industrial waste gas; a SOEC (Solid oxide electrolysis Cell) system, which communicates with the dehydration treatment apparatus to electrolyze water vapor to obtain hydrogen and oxygen in the SOEC system; a first desulfurization treatment device communicated with the residual gas to perform desulfurization treatment on the residual gas to obtain high-purity CO₂A gas; a second desulfurization treatment device communicated with the natural gas to perform desulfurization treatment on the natural gas to obtain high-purity CH₄A gas; a double reforming system connected downstream of the SOEC system, comprising a first reaction chamber and a second reaction chamber, wherein the first reaction chamber is respectively connected with a first desulfurization treatment device and the SOEC system to utilize high purity CO₂The gas and hydrogen are subjected to inverse water-gas shift reaction to prepare synthesis gas, and the second reaction chamber is respectively connected with a second desulfurization treatment device and an SOEC system to utilize high-purity CH₄The gas and oxygen are subjected to partial oxidation reaction to prepare synthesis gas.

Preferably, the hydrogen and the steam mixed gas of the SOEC system are separated at high temperature by a metal Pd membrane separator to obtain the hydrogen. More preferably, the gas outlet pipes of the hydrogen and the oxygen of the SOEC system and the connection part of the gas inlet pipe and the gas inlet of the metal Pd membrane separator are both sprayed with insulating materials.

Preferably, the first desulfurization treatment device is connected to the downstream of the SOEC system to perform hydrodesulfurization of the residual gas by using a part of hydrogen obtained by the SOEC system, wherein a part of hydrogen obtained by the SOEC system is used as a raw material for desulfurization treatment to react with sulfur-containing compounds in the residual gas to complete desulfurization.

Preferably, the second desulfurization treatment device is connected downstream of the SOEC system to perform hydrodesulfurization of the natural gas by using another part of hydrogen obtained by the SOEC system, wherein the another part of hydrogen obtained by the SOEC system is used as a desulfurization treatment raw material to react with sulfur-containing compounds in the natural gas to complete desulfurization.

Preferably, high purity CO₂Gas and/or high purity CH₄The sulfur content of the gas was below 0.1ppm each.

Preferably, the device also comprises a gas separation system connected downstream of the double reforming system, and the mixed gas from the first reaction chamber and the second reaction chamber enters the gas separation system to separate the synthesis gas.

Preferably, the gas separation system comprises a low-pressure storage tank, a booster pump and a pressure swing adsorption gas separation device, wherein the low-pressure storage tank is communicated with the first reaction chamber and the second reaction chamber to store the synthesis gas and the unreacted CO prepared by the first reaction chamber and the second reaction chamber₂A booster pump for boosting is arranged between the low-pressure storage tank and the pressure swing adsorption gas separation device to convey the boosted mixed gas to the pressure swing adsorption gas separation device, the pressure swing adsorption gas separation device for separating the mixed gas is communicated with the first reaction chamber and the second reaction chamber, and the separated unreacted CO is₂The gas is returned to the first reaction chamber and the separated unreacted natural gas is returned to the second reaction chamber.

Preferably, the apparatus further comprises a thermal management system coupled to the SOEC system and the first reaction chamber to provide thermal energy, and coupled to the second reaction chamber to recover the thermal energy.

The invention also provides a method for preparing synthesis gas with the assistance of the high-temperature electrochemical device, which comprises the following steps: separating water vapor from the industrial waste gas by a dehydration treatment device to obtain residual gas; electrolyzing the water vapor through a SOEC system to obtain hydrogen and oxygen; the residual gas is desulfurized by a first desulfurization treatment device to obtain high-purity CO₂A gas; the natural gas is desulfurized by a second desulfurization treatment device to obtain high-purity CH₄A gas; high purityCO₂Gas and hydrogen are subjected to inverse water gas shift reaction in a first reaction chamber of the double-integrated system to prepare synthesis gas, high-purity CH₄The gas and oxygen are subjected to partial oxidation reaction in a second reaction chamber of the double whole system to prepare the synthesis gas.

Preferably, the flow rate of water vapour entering the SOEC system is from 0.1MpaG to 5.0MpaG, preferably from 0.2MpaG to 0.25 MpaG.

Preferably, the flow rate molar ratio of the residual gas entering the first desulfurization treatment device to the hydrogen entering the first desulfurization treatment device is 1:1-20:1, preferably 8:1-10: 1.

Preferably, the flow molar ratio of the natural gas entering the second desulfurization treatment device to the hydrogen entering the second desulfurization treatment device is 6:1 to 20:1, preferably 9:1 to 11: 1.

Preferably, the high purity CO entering the first reaction chamber₂The molar ratio of the flow rate of the gas to the flow rate of the hydrogen gas entering the first reaction chamber is 0.1:1 to 3:1, preferably 1.5:1 to 2: 1.

Preferably, high purity CH entering the second reaction chamber₄The molar ratio of the flow of gas to oxygen entering the second reaction chamber is 0.1:1 to 3:1, preferably 1.3:1 to 1.7: 1.

Preferably, the mixed gas from the first reaction chamber and the second reaction chamber enters a gas separation system to separate the synthesis gas from the unreacted CO₂Separating gas and unreacted natural gas, and subjecting the synthetic gas to pressure swing separation to obtain H₂The ratio/CO is in the range of 1 to 5.

Preferably, the SOEC system operates at a temperature of 550 deg.C to 850 deg.C. More preferably, the current applied across the cell is between 0.1A and 100A, preferably between 10A and 20A; the voltage is 0.1V-10V, preferably 0.6V-1V.

According to the device for preparing the synthesis gas with the assistance of the high-temperature electrochemical device, the synthesis gas (H) with different proportions can be prepared by utilizing the industrial waste gas and the natural gas through the coupling of the SOEC system and the double reforming system₂CO), the final product H can be varied by adjusting the ratio of the starting materials₂The composition of the CO synthetic gas can realize the reutilization of industrial waste gas and reduce carbon emission, and can also prepare the synthetic gas and change waste into valuable.

Compared with the prior art that CO is introduced into the negative electrode₂According to the solid oxidation electrolytic cell, only water vapor is introduced into the negative electrode, and hydrogen and oxygen are generated, so that the problems of carbon deposition and the like do not exist. Compared with the double integral system which needs to additionally introduce hydrogen and oxygen in the prior art, the invention utilizes the self-produced high-purity hydrogen and oxygen in the system without additionally increasing the equipment investment. In addition, the SOEC system of the invention is combined with a double integral system to overcome a plurality of technical problems: firstly, pure hydrogen and high-temperature steam are generated at the outlet of the SOEC system, and the excessive steam can cause the catalyst in the double reforming system to generate the phenomenon of 'poisoning' so as to reduce the catalytic activity of the catalyst and finally make the catalyst bed lose efficacy, so that the product of the previous system needs to be pretreated₂Molecules are separated at high temperature, the process is different from the traditional low-temperature steam liquefaction separation process, the heat loss of gas cannot be caused, the complex process of reheating when double whole systems use hydrogen is avoided, and the perfect coupling operation of the double systems can be realized; secondly, the SOEC system is in a high-temperature and high-current working state, and electrification treatment is carried out by coupling the electrified SOEC system with a high-flammability double-integrated system (in the SOEC system H)₂And O₂The joint of the gas outlet pipe and the gas inlet of the metal Pd membrane separator is sprayed with an insulating material, so that the sealing and current insulation effects of the pipeline are realized, and the operation can be carried out more safely and efficiently; finally, the treatment of the industrial waste gas is a treatment process with complex process, high technical difficulty and high cost, and mainly the desulfurization treatment of the sulfide in the industrial waste gas needs to consume a large amount of hydrogen to clean the desulfurizer.

Drawings

Fig. 1 is an overall schematic diagram of a high temperature electrochemical device assisted synthesis gas production apparatus according to the present invention.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.