CN210150733U - Combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas - Google Patents

Combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas Download PDF

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CN210150733U
CN210150733U CN201920906400.7U CN201920906400U CN210150733U CN 210150733 U CN210150733 U CN 210150733U CN 201920906400 U CN201920906400 U CN 201920906400U CN 210150733 U CN210150733 U CN 210150733U
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carbon dioxide
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flue gas
nitrogen
gas outlet
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林千果
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

The utility model provides a combined recovery device of carbon dioxide, nitrogen and oxygen in flue gas. The apparatus comprises a first CO2Membrane separation Unit, N2Pressure swing adsorption separation unit and secondary CO2Membrane separation unit, first CO2Membrane separationThe unit is provided with a flue gas inlet, a first carbon dioxide enriched gas outlet and a first high-pressure non-permeate gas outlet; n is a radical of2The pressure swing adsorption separation unit is provided with a first high-pressure non-permeable gas inlet, a nitrogen enriched gas outlet and a nitrogen removal gas outlet, and the first high-pressure non-permeable gas inlet is connected with the first high-pressure non-permeable gas outlet; second CO2The membrane separation unit is provided with a nitrogen removal gas inlet, a second carbon dioxide enriched gas outlet and an oxygen enriched gas outlet, and the nitrogen removal gas inlet is connected with the nitrogen removal gas outlet. Utilize the device to handle the flue gas, the enrichment degree of carbon dioxide is higher, and can separate nitrogen gas and oxygen in the flue gas simultaneously, realizes the resource recovery of carbon dioxide, nitrogen gas and oxygen in the flue gas simultaneously.

Description

Combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas
Technical Field
The utility model relates to a technical field is handled to the flue gas, particularly, relates to a joint recovery unit of carbon dioxide, nitrogen gas and oxygen in flue gas.
Background
Global warming is one of the major environmental problems in the world today, among the various greenhouse gases that cause climate change, carbon dioxide (CO)2) Has the greatest influence on the temperature rise of the earth and controls CO2Emissions have become one of the important technical routes to cope with climate warming. CO in combustion flue gas2The emission has the characteristics of low concentration, stability, large concentration and amount and the like, and is used for reducing CO emission in a large scale2One of the best fields of the invention. Meanwhile, the flue gas also contains a large amount of nitrogen (N) with the concentration of about 70 percent2) And oxygen (O) at a concentration of 8%2) The concentration is lower than that of nitrogen and oxygen in air, and thus it is difficult to use.
High purity CO2Is an important industrial gas, and CO separated and trapped2The method can be injected into petroleum and natural gas fields to improve the oil gas recovery ratio, and can also be widely used for synthesizing organic compounds, manufacturing carbonated beverages and the like to realize resource utilization. CO in flue gas2The separation and trapping technology has wide application prospect and has obvious environmental protection benefit, economic benefit and social benefit. Thus, CO is separated and trapped2The technology is an important technology related to the emission reduction of greenhouse gases in coal-fired power plants.
At present, CO2Among the methods of collection and recovery of (2), the membrane separation method is one of the more effective methods. The main principle of membrane separation is that when a mixture of two or more gases passes through a polymeric membrane, the relative permeation rates of the different gases in the membrane are different due to the difference in solubility and diffusion coefficients of the various gases in the membrane. Wherein gases with relatively fast permeation rates, such as carbon dioxide, water vapor, hydrogen, helium, hydrogen sulfide, etc., can be preferentially enriched by the permeable membrane; the gas with relatively slow permeation rate, such as methane, nitrogen, carbon monoxide, etc., is enriched at the detention side of the membrane, so as to achieve the purpose of separating the mixed gas. Membrane separation for CO capture, in contrast to other methods2The device has the advantages of no chemical reaction, no pollutant generation, compact equipment structure, small occupied area, flexible starting, convenient maintenance and operation and the like.
However, because the content of nitrogen and oxygen in the flue gas is high, and the relative permeation rates of oxygen and nitrogen in the membrane are small, residual CO still exists when the flue gas is treated by the membrane separation method2A number of problems, which also result in CO2Low enrichment degree, difficult separation of nitrogen and oxygen and much resource waste.
SUMMERY OF THE UTILITY MODEL
The main object of the utility model is to provide a combined recovery unit of carbon dioxide, nitrogen gas and oxygen in flue gas to when utilizing the membrane separation method to handle the flue gas among the solution prior art, CO2Low enrichment degree and difficult separation of nitrogen and oxygen.
In order to achieve the above object, according to an aspect of the present invention, there is provided a combined recovery apparatus for carbon dioxide, nitrogen and oxygen in flue gas, comprising: first CO2The membrane separation unit is provided with a flue gas inlet, a first carbon dioxide enriched gas outlet and a first high-pressure non-permeate gas outlet; n is a radical of2The pressure swing adsorption separation unit is provided with a first high-pressure non-permeable gas inlet, a nitrogen enriched gas outlet and a nitrogen removal gas outlet, and the first high-pressure non-permeable gas inlet is connected with the first high-pressure non-permeable gas outlet; and a second CO2And the membrane separation unit is provided with a nitrogen degassing inlet, a second carbon dioxide enriched gas outlet and an oxygen enriched gas outlet, and the nitrogen degassing inlet is connected with the nitrogen degassing outlet.
Further, the apparatus further comprises a third CO2Membrane separation unit, tertiary CO2The membrane separation unit is provided with a first carbon dioxide enriched gas inlet and CO2The product gas outlet, the first carbon dioxide enriched gas inlet and the first carbon dioxide enriched gas outlet are connected.
Further, tertiary CO2The membrane separation unit is also provided with a second high-pressure non-permeate gas outlet, and the first high-pressure non-permeate gas inlet and the first high-pressure non-permeate gas outlet are used for transmitting non-permeate gasThe delivery pipeline is connected, and the second high-pressure non-permeate gas outlet is connected with the non-permeate gas delivery pipeline.
Further, the first carbon dioxide enriched gas inlet and the first carbon dioxide enriched gas outlet are connected through a carbon dioxide enriched gas conveying pipeline, and the second carbon dioxide enriched gas outlet is connected with the carbon dioxide enriched gas conveying pipeline.
Further, the device also comprises a first compression unit, wherein the first compression unit is arranged on the air inlet pipeline where the flue gas inlet is located and used for compressing the flue gas.
Further, the device also comprises a first flue gas treatment unit, wherein the first flue gas treatment unit is arranged on a pipeline connected with the first compression unit and the flue gas inlet and used for removing solid impurities and liquid impurities in the compressed flue gas.
Further, the first flue gas treatment unit comprises a first cooler, a first demister and a first filter which are arranged in series.
Furthermore, the device also comprises a second compression unit, the second compression unit is arranged on the carbon dioxide enriched gas conveying pipeline, a second carbon dioxide enriched gas outlet is connected to the carbon dioxide enriched gas conveying pipeline at the upstream of the second compression unit, and the second compression unit is used for compressing the carbon dioxide enriched gas discharged from the first carbon dioxide enriched gas outlet and the second carbon dioxide enriched gas outlet.
Furthermore, the device also comprises a second flue gas treatment unit, the second flue gas treatment unit is arranged on the carbon dioxide enriched gas conveying pipeline between the second compression unit and the first carbon dioxide enriched gas inlet, and the second flue gas treatment unit is used for removing moisture in the compressed carbon dioxide enriched gas.
Further, the second flue gas treatment unit comprises a second cooler, a second demister and a second filter which are arranged in series, or the second flue gas treatment unit is a dewatering device.
Further, the second carbon dioxide enriched gas outlet is connected with the carbon dioxide enriched gas conveying pipeline through the carbon dioxide enriched gas branch pipe; the apparatus further comprises a third compression unit disposed on the carbon dioxide rich gas branch.
Further, the device also comprises a third flue gas treatment unit, wherein the third flue gas treatment unit is arranged on a pipeline connected with the nitrogen desorption gas inlet and the nitrogen desorption gas outlet and is used for removing moisture in the nitrogen desorption gas discharged from the nitrogen desorption gas outlet.
Further, the third flue gas treatment unit comprises a third cooler, a third demister and a third filter which are arranged in series, or the third flue gas treatment unit is a dewatering device.
The utility model provides a combined recovery device of carbon dioxide, nitrogen gas and oxygen in flue gas, it includes first CO2Membrane separation Unit, N2Pressure swing adsorption separation unit and secondary CO2Membrane separation unit, first CO2The membrane separation unit is provided with a flue gas inlet, a first carbon dioxide enriched gas outlet and a first high-pressure non-permeate gas outlet; n is a radical of2The pressure swing adsorption separation unit is provided with a first high-pressure non-permeable gas inlet, a nitrogen enriched gas outlet and a nitrogen removal gas outlet, and the first high-pressure non-permeable gas inlet is connected with the first high-pressure non-permeable gas outlet; second CO2The membrane separation unit is provided with a nitrogen removal gas inlet, a second carbon dioxide enriched gas outlet and an oxygen enriched gas outlet, and the nitrogen removal gas inlet is connected with the nitrogen removal gas outlet.
Utilize above-mentioned device to handle the flue gas, the enrichment degree of carbon dioxide is higher, and can separate nitrogen gas and oxygen in the flue gas simultaneously, realizes the resource recovery of carbon dioxide, nitrogen gas and oxygen in the flue gas simultaneously.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic diagram of a combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas according to an embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. first CO2A membrane separation unit; 20. n is a radical of2A pressure swing adsorption separation unit; 30. second CO2A membrane separation unit; 40. third CO2A membrane separation unit; 50. a first compression unit; 60. a first flue gas treatment unit; 70. a second compression unit; 80. a second flue gas treatment unit; 90. a third compression unit; 100. and the third flue gas treatment unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background section, CO is present in the prior art when flue gas is treated using membrane separation2Low enrichment degree and difficult separation of nitrogen and oxygen.
In order to solve the above problem, the present invention provides a combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas, as shown in fig. 1, comprising a first CO2 Membrane separation unit 10, N2Pressure swing adsorption separation unit 20 and secondary CO2 Membrane separation unit 30, first CO2The membrane separation unit 10 is provided with a flue gas inlet, a first carbon dioxide enriched gas outlet and a first high-pressure non-permeate gas outlet; n is a radical of2The pressure swing adsorption separation unit 20 is provided with a first high-pressure non-permeable gas inlet, a nitrogen enriched gas outlet and a nitrogen removal gas outlet, and the first high-pressure non-permeable gas inlet is connected with the first high-pressure non-permeable gas outlet; second CO2The membrane separation unit 30 is provided with a nitrogen degassing inlet, a second carbon dioxide enriched gas outlet and an oxygen enriched gas outlet, and the nitrogen degassing inlet is connected with the nitrogen degassing outlet.
Different from the traditional membrane separation method, the utility model discloses a flue gas is handled to the device that membrane separation and pressure swing adsorption separation combined together. Specifically, the method comprises the following steps:
using a first CO2The membrane separation unit 10 may first subject the flue gas to CO2The first CO is utilized because of the huge amount of flue gas required for carbon capture in the membrane separation treatment2The membrane separation unit 10 advantageously reduces the footprint and simplifies the process. In the first CO2Under the treatment of the membrane separation unit 10, most of the carbon dioxide in the flue gas forms a first carbon dioxide enriched gas through the separation membrane and is discharged from a first carbon dioxide enriched gas outlet, and oxygen, nitrogen and a small amount of carbon dioxide form a first high-pressure non-permeate gas and are discharged.
Secondly, use of N2The pressure swing adsorption separation unit 20 may perform pressure swing adsorption separation on nitrogen in the first high pressure non-permeate gas. N is a radical of2The pressure swing adsorption separation unit 20 performs nitrogen adsorption based on the adsorption rate difference separation of the adsorbent for nitrogen, oxygen, and carbon dioxide. And undergoes the first CO2Most of the carbon dioxide in the flue gas is separated out through the treatment of the membrane separation unit 10, and the concentration of the carbon dioxide in the first high-pressure non-permeable gas is obviously reduced, so that the influence of high-concentration carbon dioxide on the pressure swing adsorption of nitrogen is favorably reduced. Compared with other methods, the pressure swing adsorption has the advantages of no chemical reaction, no pollutant generation, simple operation, convenient maintenance and operation, and the like.
Warp of N2After the pressure swing adsorption separation unit 20 is used for processing, nitrogen in the first high-pressure non-permeate gas is separated and removed, and nitrogen degassing gas consisting of oxygen and a small amount of carbon dioxide enters second CO2The membrane separation unit 30 performs further CO2Membrane separation, so that oxygen enriched gas with higher purity can be obtained; another portion of the carbon dioxide enriched gas.
Utilize the utility model discloses foretell device handles the flue gas, realizes the resource recovery of carbon dioxide, nitrogen gas and oxygen in the flue gas simultaneously.
In a preferred embodiment, N2The pressure swing adsorption separation unit 20 comprises N2Pressure swing adsorption unit and N2Desorption unit, N2The pressure swing adsorption unit is used for the pair of N2Performing pressure swing adsorption, N2The desorption unit is used for adsorbing the dioxygenDesorbing the adsorbent after the carbonization. The specific desorption method may be vacuum evacuation or the like.
In a preferred embodiment, as shown in FIG. 1, the apparatus further comprises a third CO2 Membrane separation unit 40, third CO2The membrane separation unit 40 is provided with a first carbon dioxide enriched gas inlet and CO2The product gas outlet, the first carbon dioxide enriched gas inlet and the first carbon dioxide enriched gas outlet are connected. Using tertiary CO2The membrane separation unit 40 can further enrich the carbon dioxide in the first carbon dioxide enriched gas to form a carbon dioxide product gas.
In a preferred embodiment, the first CO2 Membrane separation Unit 10, second CO2 Membrane separation unit 30 and tertiary CO2The membrane modules in the membrane separation unit 40 are each independently selected from hollow fiber membranes, spiral wound membranes or plate membranes. Here, "independently selected from" means that the first CO is2 Membrane separation Unit 10, second CO2 Membrane separation unit 30 and tertiary CO2The membrane modules in the membrane separation unit 40 are each selected from one of the three membrane modules, and the three membrane modules may be identical to or different from each other. Preferably, the material of the membrane module is a high molecular polymer organic material. Compared with an inorganic membrane as a membrane component, the membrane component formed by adopting the high-molecular polymer organic material has the advantages of simple processing technology and lower manufacturing cost, and is used for separating CO in flue gas on a large scale2The project investment cost can be greatly reduced. Meanwhile, the concentration of carbon dioxide in certain flue gas such as flue gas of a coal-fired power plant is low (about 12 percent), the selectivity of the organic membrane is higher, and CO can be further improved2Separation recovery rate and trapping amount.
In a preferred embodiment, the third CO2The membrane separation unit 40 is further provided with a second high-pressure non-permeate gas outlet, the first high-pressure non-permeate gas inlet is connected with the first high-pressure non-permeate gas outlet through a non-permeate gas conveying pipeline, and the second high-pressure non-permeate gas outlet is connected with the non-permeate gas conveying pipeline. Thus, the third CO can be introduced2The high pressure non-permeate gas and the first CO separated by the membrane separation unit 402Height separated by the membrane separation unit 10Pressing the non-permeate gas together to perform N2Pressure swing adsorption separation is carried out, so that nitrogen and oxygen in the flue gas are further recovered.
To further recover carbon dioxide, in a preferred embodiment, the first carbon dioxide-enriched gas inlet and the first carbon dioxide-enriched gas outlet are connected by a carbon dioxide-enriched gas delivery line, and the second carbon dioxide-enriched gas outlet is connected to the carbon dioxide-enriched gas delivery line. Thus, the second CO can be introduced2The carbon dioxide enriched gas and the first CO separated by the membrane separation unit 302The carbon dioxide enriched gas separated by the membrane separation unit 10 is further subjected to membrane separation together with the carbon dioxide enriched gas to enrich the carbon dioxide, so that carbon dioxide product gas is obtained.
In a preferred embodiment, the device further comprises a first compression unit 50, and the first compression unit 50 is arranged on the air inlet pipeline where the flue gas inlet is located and used for compressing the flue gas. Can be a first CO using the first compression unit 502CO of the Membrane separation Unit 102Osmosis further provides pressure drive. And it should be noted that the present invention utilizes the first compression unit 50 to provide sufficient pressure differential to drive sufficient CO compared to a vacuum or purge depressurization method on the permeate side2Permeation through membranes, especially organic membranes, to further increase CO2The collection and recovery rate of (1). In the same way, preferably, the apparatus further comprises a second compression unit 70, the second compression unit 70 is disposed on the carbon dioxide enriched gas transmission pipeline, and the second carbon dioxide enriched gas outlet is connected to the carbon dioxide enriched gas transmission pipeline upstream of the second compression unit 70, and the second compression unit 70 is configured to compress the carbon dioxide enriched gas discharged from the first carbon dioxide enriched gas outlet and the second carbon dioxide enriched gas outlet.
Besides carbon dioxide, oxygen and nitrogen, the flue gas also carries some solid impurities (particles) and liquid impurities (moisture), and in order to reduce the solid impurities and the liquid impurities to the first CO2The influence of the separation membranes, in particular the organic separation membranes, in the membrane separation unit 10, in a preferred embodiment the above-described apparatus further comprises a first flue gas treatment unit 60, a second flue gas treatment unitA flue gas treatment unit 60 is disposed on the pipeline connecting the first compression unit 50 and the flue gas inlet, and is used for removing solid impurities and liquid impurities in the compressed flue gas. The separation membrane, especially the organic separation membrane, is easily polluted by solid impurities such as particles and has high requirements on humidity and temperature, and the influence can be reduced as much as possible by using the first flue gas treatment unit 60, so that the flue gas treatment effect is further improved.
In one embodiment, solid and liquid impurities in the flue gas may be removed using a filter. More preferably, the first flue gas treatment unit 60 comprises a first cooler, a first demister, and a first filter arranged in series. The liquid in the flue gas can be further condensed by using the first cooler, then the condensable liquid foam, fog drops and possibly entrained solid particles in the flue gas are removed by using the first demister, and finally harmful impurities such as possibly entrained fine liquid and the like in the flue gas can be further removed by using the first filter. Meanwhile, the arrangement of the first cooler is also beneficial to controlling the temperature of the flue gas so as to further improve the first CO2Operational stability of the membrane separation unit 10.
In a preferred embodiment, the first flue gas treatment unit 60 further comprises a heat exchanger provided with an inlet to be heated and an outlet to be heated, the inlet to be heated being connected to the outlet of the first filter and the outlet to be heated being connected to the flue gas inlet. Therefore, the flue gas after the impurities are removed can be heated by heat exchange in the heat exchanger, so that the flue gas is far away from the dew point and the operating temperature of the system is constant.
In a preferred embodiment, the apparatus further comprises a second flue gas treatment unit 80, the second flue gas treatment unit 80 being arranged in the carbon dioxide enriched gas transfer line between the second compression unit 70 and the first carbon dioxide enriched gas inlet, the second flue gas treatment unit 80 being adapted to remove moisture from the compressed carbon dioxide enriched gas. This is advantageous for further enhancement of the tertiary CO2Operational stability of the membrane separation unit 40. Preferably, the second flue gas treatment unit 80 comprises a second cooler, a second demister and a second filter arranged in series, or the second flue gas treatment unit 80 isA dewatering device. The second cooler, second demister, and second filter function similarly to the first cooler, first demister, and first filter described above. A dehydration unit may also be utilized to remove moisture from the carbon dioxide enriched gas.
Similarly, the second flue gas treatment unit 80 preferably further comprises a heat exchanger provided with an inlet to be heated and an outlet to be heated, the inlet to be heated is connected with the outlet of the second filter, and the outlet to be heated is connected with the third CO2The first carbon dioxide-enriched gas inlet of the membrane separation unit 40 is connected.
By third CO2The pressure of the carbon dioxide enriched gas separated by the membrane separation unit 40 tends to be slightly lower, and in a preferred embodiment, the second carbon dioxide enriched gas outlet is connected to the carbon dioxide enriched gas delivery line through a carbon dioxide enriched gas branch pipe; the apparatus further comprises a third compression unit 90 arranged in the carbon dioxide rich gas branch.
In a preferred embodiment, the apparatus further comprises a third flue gas treatment unit 100, and the third flue gas treatment unit 100 is disposed on a pipeline connecting the nitrogen removal gas inlet and the nitrogen removal gas outlet, and is used for removing moisture in the nitrogen removal gas discharged from the nitrogen removal gas outlet. This is advantageous for increasing the secondary CO2Operational stability of the membrane separation unit 30. Preferably, the third flue gas treatment unit 100 comprises a third cooler, a third demister and a third filter arranged in series, or the third flue gas treatment unit 100 is a dehydration device. The third cooler, third demister, and third filter function similarly to the first cooler, first demister, and first filter described above.
Preferably, the third flue gas treatment unit 100 further comprises a heat exchanger provided with an inlet to be heated and an outlet to be heated, the inlet to be heated is connected with the outlet of the third filter, and the outlet to be heated is connected with the second CO2The nitrogen degassing inlet of the membrane separation unit 30 is connected.
The device is not only suitable for treating the flue gas of a coal-fired power plant, but also suitable for separating and trapping carbon dioxide, oxygen and nitrogen in low-concentration flue gas of steel plants, cement plants and the like.
According to another aspect of the present invention, there is provided a method for recovering carbon dioxide, nitrogen and oxygen from flue gas, comprising the steps of: subjecting the flue gas to first CO2Membrane separation treatment is carried out to obtain a first part of carbon dioxide enriched gas and a first high-pressure non-permeate gas; performing nitrogen pressure swing adsorption separation on the first high-pressure non-permeate gas to obtain nitrogen enriched gas and nitrogen degassing gas; and degassing the nitrogen gas for a second CO2Membrane separation treatment to obtain oxygen-enriched gas and a second portion of carbon dioxide-enriched gas. By using the method provided by the utility model, CO is added2The membrane separation and the nitrogen pressure swing adsorption are combined, and the resource recovery of carbon dioxide, nitrogen and oxygen in the flue gas is realized.
To further enhance the effectiveness of nitrogen pressure swing adsorption separation, in a preferred embodiment, the process conditions during nitrogen pressure swing adsorption separation are as follows: the treatment temperature is-10-120 ℃, the treatment pressure is 0.10-1.50 MPa (absolute pressure), and the adsorbent is one or more of activated carbon, silica gel, molecular sieve and modified adsorbent thereof. Preferably, the nitrogen pressure swing adsorption separation step comprises: performing nitrogen pressure swing adsorption on the first high-pressure non-permeate gas by using the adsorbent under the process conditions to obtain nitrogen degassing gas and the adsorbent adsorbed with nitrogen; and desorbing the adsorbent adsorbed with the nitrogen in a vacuum state to obtain nitrogen enriched gas.
To further enhance the carbon dioxide enrichment, in a preferred embodiment, the first portion of the carbon dioxide-enriched gas and the second portion of the carbon dioxide-enriched gas are mixed to form a carbon dioxide-enriched gas, and the method further comprises subjecting the carbon dioxide-enriched gas to a third CO enrichment2Membrane separation treatment to obtain CO2And (5) producing gas.
In order to further increase the enrichment effect of nitrogen and oxygen, in a preferred embodiment, a third CO2A second high-pressure non-permeate gas is also obtained in the membrane separation treatment process, and the method also comprises the step of carrying out nitrogen pressure swing adsorption separation on the second high-pressure non-permeate gas and the first high-pressure non-permeate gas。
In a preferred embodiment, the flue gas is subjected to a first CO treatment2Before the membrane separation treatment, the method also comprises a step of performing first compression on the flue gas, preferably the first compression step is performed to ensure that the gas pressure is more than 0.11MPa (A). Thus may be first CO2CO treated by membrane separation2Osmosis further provides pressure drive. For the same reason, it is preferable to perform CO for the third time2Before the membrane separation treatment process, the method also comprises the step of carrying out secondary compression on the carbon dioxide enriched gas; preferably, in the second compression step, the gas pressure is greater than 0.11MPa (A). More preferably, the method further comprises, prior to the step of mixing the first portion of the carbon dioxide-enriched gas and the second portion of the carbon dioxide-enriched gas to form the carbon dioxide-enriched gas, the step of compressing the second portion of the carbon dioxide-enriched gas; preferably, the step of compressing the second portion of the carbon dioxide-enriched gas is carried out such that the gas pressure is greater than 0.11mpa (a).
Besides carbon dioxide, oxygen and nitrogen, the flue gas also carries solid impurities (particles) and liquid impurities (moisture), and in order to reduce the solid impurities and the liquid impurities to CO for the first time2Influence of membrane separation process, in a preferred embodiment, after the step of first compressing, the method further comprises the step of treating the compressed flue gas to remove solid and liquid impurities therein; preferably, the step of treating the compressed flue gas comprises: and cooling, demisting and filtering the compressed flue gas in sequence. After the flue gas is cooled, condensable liquid foam, fog drops and possibly entrained solid particles in the flue gas can be removed through demisting. And then harmful impurities such as fine liquid and the like possibly carried in the raw material gas can be further removed through filtration treatment. In short, the above method can remove impurities such as liquid impurities and solid particles in the flue gas more sufficiently, thereby further improving the carbon dioxide capturing effect. Meanwhile, the temperature of the flue gas can be effectively controlled by cooling the flue gas, so that the operation stability of the separation membrane, particularly the organic separation membrane, is further improved.
In a preferred embodiment, after the step of second compressing, the method further comprises the step of removing moisture from the compressed carbon dioxide-enriched gas; preferably, the step of removing moisture from the compressed carbon dioxide-enriched gas comprises sequentially cooling, demisting and filtering the compressed carbon dioxide-enriched gas, or dehydrating the compressed carbon dioxide-enriched gas.
In a preferred embodiment, the method further comprises, prior to the step of nitrogen pressure swing adsorption separation, the step of removing moisture from the first high pressure non-permeate gas; preferably, the step of removing moisture from the first high pressure non-permeate gas comprises: and sequentially cooling, demisting and filtering the first high-pressure non-permeable gas, or dehydrating the first high-pressure non-permeable gas.
The following examples further illustrate the beneficial effects of the present invention:
example 1
The device shown in the figure 1 of the utility model balances the low concentration CO in the flue gas by testing the flue gas of a certain steel plant2Trapping of the process and recovery of oxygen and nitrogen.
Wherein, the carbon dioxide membrane separation units are all hollow fiber membranes made of organic membrane materials; in the step of nitrogen pressure swing adsorption separation, the process conditions are as follows: the treatment temperature is 30 ℃, the treatment pressure is 0.47MPa (A), and the adsorbent is a carbon molecular sieve.
The mass balance results are shown in table 1:
TABLE 1
Figure BDA0002095668810000081
From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: as can be seen from Table 1, when the blast furnace flue gas flow rate to be treated was 10000Nm3/h，CO2Content 27.35%, O2Content 6.23%, N2At 65.99%, in the treatment process of this example, the second stage CO2Permeate (product) gas flow to membrane separation unitIs 628Nm3/h，CO2The content is improved from 27.35% to 90.11%. N is a radical of2The flow of the adsorption gas from the pressure swing adsorption device is 6393.40Nm3/h，N2The content is increased from 65.99% to 97.10%. The flow rate of the permeate of the membrane separation unit in the third stage is 921Nm3/h，CO2The content is improved from 40.18 percent to 98.50 percent. O is2The content is increased from 6.23% to 36.43%. Utilize above-mentioned device to handle the flue gas, the enrichment degree of carbon dioxide is higher, and can separate nitrogen gas and oxygen in the flue gas simultaneously, realizes the resource recovery of carbon dioxide, nitrogen gas and oxygen in the flue gas simultaneously.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. A combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas is characterized by comprising:
first CO2The membrane separation unit (10) is provided with a flue gas inlet, a first carbon dioxide enriched gas outlet and a first high-pressure non-permeation gas outlet;
N2the pressure swing adsorption separation unit (20) is provided with a first high-pressure non-permeable gas inlet, a nitrogen enriched gas outlet and a nitrogen removal gas outlet, and the first high-pressure non-permeable gas inlet is connected with the first high-pressure non-permeable gas outlet; and
second CO2And the membrane separation unit (30) is provided with a nitrogen degassing inlet, a second carbon dioxide enriched gas outlet and an oxygen enriched gas outlet, and the nitrogen degassing inlet is connected with the nitrogen degassing outlet.
2. The apparatus of claim 1, further comprising a third CO2A membrane separation unit (40), the third CO2The membrane separation unit (40) is providedHaving a first carbon dioxide enriched gas inlet and CO2A product gas outlet, the first carbon dioxide enriched gas inlet and the first carbon dioxide enriched gas outlet being connected.
3. The apparatus of claim 2, wherein the third CO is2The membrane separation unit (40) is also provided with a second high-pressure non-permeate gas outlet, the first high-pressure non-permeate gas inlet is connected with the first high-pressure non-permeate gas outlet through a non-permeate gas conveying pipeline, and the second high-pressure non-permeate gas outlet is connected with the non-permeate gas conveying pipeline.
4. The apparatus of claim 2, wherein the first carbon dioxide-enriched gas inlet and the first carbon dioxide-enriched gas outlet are connected by a carbon dioxide-enriched gas delivery line, and the second carbon dioxide-enriched gas outlet is connected to the carbon dioxide-enriched gas delivery line.
5. The device according to any one of claims 1 to 4, further comprising a first compression unit (50), said first compression unit (50) being arranged on the inlet duct where the flue gas inlet is located for compressing the flue gas.
6. The apparatus according to claim 5, further comprising a first flue gas treatment unit (60), wherein the first flue gas treatment unit (60) is arranged on a pipeline connecting the first compression unit (50) and the flue gas inlet, and is used for removing solid impurities and liquid impurities in the compressed flue gas.
7. The apparatus according to claim 6, wherein the first flue gas treatment unit (60) comprises a first cooler, a first demister and a first filter arranged in series.
8. The apparatus of claim 4, further comprising a second compression unit (70), the second compression unit (70) being disposed in the carbon dioxide enriched gas delivery line and the second carbon dioxide enriched gas outlet being connected to the carbon dioxide enriched gas delivery line upstream of the second compression unit (70), the second compression unit (70) being configured to compress the carbon dioxide enriched gas discharged from the first and second carbon dioxide enriched gas outlets.
9. The apparatus according to claim 8, further comprising a second flue gas treatment unit (80), the second flue gas treatment unit (80) being arranged in the carbon dioxide enriched gas transfer line between the second compression unit (70) and the first carbon dioxide enriched gas inlet, the second flue gas treatment unit (80) being adapted to remove moisture from the compressed carbon dioxide enriched gas.
10. The apparatus according to claim 9, wherein the second flue gas treatment unit (80) comprises a second cooler, a second demister and a second filter arranged in series, or wherein the second flue gas treatment unit (80) is a dewatering device.
11. The apparatus of any one of claims 8 to 10, wherein the second carbon dioxide-enriched gas outlet is connected to the carbon dioxide-enriched gas delivery line by a carbon dioxide-enriched gas branch line; the apparatus also includes a third compression unit (90) disposed on the carbon dioxide-rich gas branch pipe.
12. The plant according to any of claims 1 to 4, characterized in that it further comprises a third flue gas treatment unit (100), said third flue gas treatment unit (100) being arranged on the line connecting the nitrogen degassing gas inlet and the nitrogen degassing gas outlet for removing moisture from the nitrogen degassing gas discharged from the nitrogen degassing gas outlet.
13. The apparatus according to claim 12, wherein the third flue gas treatment unit (100) comprises a third cooler, a third demister and a third filter arranged in series, or wherein the third flue gas treatment unit (100) is a dewatering device.
CN201920906400.7U 2019-06-14 2019-06-14 Combined recovery device for carbon dioxide, nitrogen and oxygen in flue gas Active CN210150733U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110127700A (en) * 2019-06-14 2019-08-16 林千果 The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110127700A (en) * 2019-06-14 2019-08-16 林千果 The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen

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