CN113521970A - For CO2Membrane absorption method for trapping and utilization - Google Patents

For CO2Membrane absorption method for trapping and utilization Download PDF

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Publication number
CN113521970A
CN113521970A CN202110813728.6A CN202110813728A CN113521970A CN 113521970 A CN113521970 A CN 113521970A CN 202110813728 A CN202110813728 A CN 202110813728A CN 113521970 A CN113521970 A CN 113521970A
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gas
carbon dioxide
fiber membrane
alkali solution
hollow fiber
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CN202110813728.6A
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Chinese (zh)
Inventor
刘清才
曾靖淞
黄爱军
刘艺
曹俊
冉雅郡
顾咸志
杨剑
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New Zhongtian Environmental Protection Engineering Chongqing Co ltd
Chongqing University
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New Zhongtian Environmental Protection Engineering Chongqing Co ltd
Chongqing University
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Priority to CN202110813728.6A priority Critical patent/CN113521970A/en
Publication of CN113521970A publication Critical patent/CN113521970A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D2053/221—Devices
    • B01D2053/223—Devices with hollow tubes
    • B01D2053/224—Devices with hollow tubes with hollow fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention discloses a method for preparing CO2A film absorption method for trapping and utilizing relates to the technical field of separating carbon dioxide in flue gas. The invention aims to effectively improve CO in flue gas2Separation and capture of CO by one-step method2Emission reduction and product preparation. Adopting composite alkali absorption liquid (NaOH/NH)4OH) is carried out by capturing carbon dioxide in the gas through a hollow fiber membrane module, and soda is produced by using the captured carbon dioxide. The gas enters a tube pass or a shell pass of a hydrophobic hollow fiber membrane absorber after being dedusted and cooled; filtering the reducing solution, then entering a shell pass or a tube pass of a hollow fiber membrane absorber through a cooling device to capture carbon dioxide in the gas, and entering the absorbed alkali solution into a product preparation device. The hollow fiber membrane component has a larger specific surfaceThe characteristics of the area can improve the removal rate of carbon dioxide, overcome the problems of flooding entrainment, bias flow and the like of the traditional absorption tower, and simultaneously, products such as soda and the like are prepared to form the utilization of the carbon dioxide.

Description

For CO2Membrane absorption method for trapping and utilization
Technical Field
The invention belongs to the technical field of capturing carbon dioxide in flue gas, and relates to a process method for separating carbon dioxide in gas by using a hydrophobic hollow fiber membrane absorber taking an alkali solution as a carbon dioxide absorption solution.
Background
CO2The large amount of emission causes global warming, aggravates greenhouse effect and increases the emission control of carbon dioxide in various countries of the world with frequent extreme weather. With the sign of the kyoto protocol and the call of the global climate peak of copenhagen, countries in the world pay more attention to the research, development and industrialization of carbon dioxide emission reduction technology. The government of China officially released the target for controlling the emission of greenhouse gases in 2020 in 11 and 26 months in 2009: the emission of the carbon dioxide with the total production value in China is reduced by 40-45% compared with 2005 by 2020, which means that the technology for capturing and utilizing the carbon dioxide has extremely great social and environmental significance and very wide application prospect.
CO emitted by fossil fuel combustion2About 80 percent of the total emission, wherein the flue gas of the fossil fuel power plant is a long-term stable and centralized emission source of CO2, and the CO emitted by the flue gas is discharged2Accounting for 30% of the total emissions. Approximately 20-40% of the CO produced by global fossil fuels was predicted by 20502Emissions can be technically suitable for capture, including 30-60% CO from coal-to-electricity plants2Emissions and 30-40% CO from other industries2And (5) discharging. Thereby realizing the flue gas CO of the coal-fired power plant2The large-scale capture becomes a main way for reducing the emission of greenhouse gases and is one of the ways with great potential for coping with global climate change.
The membrane absorption process combines the selectivity of chemical absorption process and the compactness of membrane separation process, and is a promising CO2And (4) a trapping process. The membrane absorption method can overcome the defects of the conventional gas-liquid contact equipment, improve the capture efficiency of the carbon dioxide, and simultaneously can use alcohol amine and the like which have good absorption and regeneration performance but are easy to degrade, thereby greatly reducing the energy consumption in the capture process. The gas treated in the membrane absorption method is not directly contacted with absorption liquid, the gas and the absorption liquid respectively flow on two sides of the membrane, the membrane per se has no selectivity on the gas, and only plays a role in isolating the gas from the absorption liquid, and micropores on the membrane can allow gas molecules separated from one side of the membrane to pass through the microporous membrane to the other side of the membrane under certain pressure and achieve the purpose of separating a certain component in the gas through the selective absorption of the absorption liquid on the other side of the membrane.
Gas permeating the microporous absorption liquid of the hollow fiber membrane, wherein CO2Is removed by rapid chemical reaction with the absorption liquid. In the process of membrane contactor removal, CO2The gas passes through one side of the hollow fiber membrane module, and the absorption liquid passes through the other side of the membrane module to be in countercurrent contact with the hollow fiber membrane module. CO22Gas diffuses from gas phase to membrane-liquid interface through micropores of membrane, and CO in gas2Chemically react with the absorption liquid to generate CO2The concentration at the membrane-liquid interface is almost zero, and CO is driven by the concentration difference2Continuously diffusing to the side of the absorption liquid to perform chemical reaction with the absorption liquid to be removed. Other components in the gas are not driven by concentration difference because of low solubility in the absorption liquid and hardly react with the absorption liquid, and cannot permeate the microporous membrane to remain in the raw material gas.
Disclosure of Invention
For CO2A membrane absorption method of trapping utilization. The method is characterized in that the alkali solution captures and absorbs carbon dioxide in gas through a hydrophobic hollow fiber membrane component, and the emission reduction of the carbon dioxide and the preparation of products are completed by a one-step method. The process comprises the following steps:
(1) gas to be treated enters a tube side or a shell side of the hollow fiber membrane component through a flue gas dedusting and cooling system and a compressor or a blower and a gas flow control system;
(2) the alkali solution enters a hollow fiber membrane module tube side or shell side through an alkali solution filtering system and a cooling system by an alkali solution pump through a flow regulating system to be absorbed by carbon dioxide;
(3) carbon dioxide in the gas reacts with the alkali solution through the surface micropores of the hollow fiber membrane to capture the dioxide in the gas; wherein, the gas flow regulating system, the gas pressure control and alkali solution flow regulating system and the alkali solution pressure regulating system ensure that gas-liquid two phases maintain a certain pressure difference for absorption, and the pressure difference is between 0.05 and 0.25 Mpa; the gas phase and the liquid phase are respectively arranged at the inner side and the outer side of the hollow fiber membrane, and are not in direct contact, so that the capture of carbon dioxide in the gas is realized;
(4) and collecting the absorbed alkali solution, and enabling the alkali solution to come out of the membrane absorber and enter a product preparation device.
Generally, the main body of the alkali solution is NaOH and NH4OH。
The hollow fiber membrane material is a hydrophobic membrane material, and a polypropylene or polytetrafluoroethylene or polyvinylidene fluoride material is selected; the micro-pore diameter of the fiber membrane is 0.02-2 μm; the porosity is 30-50%, and the film loading is 30-60%.
The product preparation device is a packed tower.
The hollow fiber membrane component of the process method has the characteristic of larger specific surface area, can improve the removal rate of carbon dioxide, overcomes the problems of flooding, entrainment, bias flow and the like of the traditional absorption tower, and simultaneously effectively reduces the contact between the alkali solution and oxygen in the flue gas and reduces the degradation loss of the alkali solution.
The process method can realize the capture of carbon dioxide and the preparation of products by a one-step method.
Drawings
FIG. 1 is a schematic diagram of a process flow for capturing carbon dioxide in gas by an alkaline solution membrane absorption method. FIG. 2 is a schematic diagram of a membrane absorber configuration in an embodiment of the invention.
In the attached drawing, 1 is a gas compressor, 2 is a flue gas dedusting and cooling system, 3 is a gas flow control system, 4 is a hydrophobic hollow fiber membrane component, 5 is an alkali solution flow control system, 6 is an alkali solution cooling system, 7 is an alkali solution filtering system, 8 is an alkali solution pump, 9 is an alkali solution, 10 is an alkali solution pump, 11 is a product production device, 12 is a flue gas inlet, 13 is a waste gas outlet, 14 is an alkali solution outlet, 15 is an alkali solution inlet, 16 is a hollow fiber membrane, and 17 is a shell pass.
Detailed Description
The present invention will be described in detail below with reference to examples and the accompanying drawings.
Example (b):
in this example, the CO2 content in the flue gas was 15%, and the flue gas amount was 3Nm3H is used as the reference value. The hollow fiber membrane component is made of polyvinylidene fluoride; the micro-pore diameter of the fiber membrane is 0.02-1 μm; the porosity is 30-40%, and the film filling rate is 40-60%.
The process method of the embodiment is as shown in figure 1, and the flue gas is sent to a membrane absorber, namely a hydrophobic hollow fiber membrane group 4, by a fan after passing through a flue gas cooling, dedusting and cooling system 2 and a gas flow control system 3.
The alkali solution enters a membrane absorber, namely the hydrophobic hollow fiber membrane group 4, after passing through an alkali solution pump 8, an alkali solution filtering system 7, an alkali solution cooling system 6 and an alkali solution flow control system 5.
Carbon dioxide in the gas reacts with the alkali solution through the surface micropores of the hollow fiber membrane to capture the dioxide in the gas; wherein, the gas-liquid two phases are absorbed by maintaining a certain pressure difference through a gas flow regulating system, a gas pressure control and alkali solution flow regulating system and an alkali solution pressure regulating system, and the pressure difference is between 0.05 and 0.25 Mpa; the gas phase and the liquid phase are respectively arranged at the inner side and the outer side of the hollow fiber membrane, and are not in direct contact, so that the capture of carbon dioxide in the gas is realized. The alkali solution for capturing the CO2 is fed to the product manufacturing apparatus 11 through the alkali solution pump 10.
According to the results of the implementation case and the comparison example, the carbon dioxide capturing and removing rate can be improved by about 30% by adopting the hollow fiber membrane module, the product preparation is completed, and the subsequent treatment is reduced.

Claims (4)

1. For CO2A membrane absorption method of trapping utilization. The method is characterized in that the alkali solution captures and absorbs carbon dioxide in gas through a hydrophobic hollow fiber membrane component, and the emission reduction of the carbon dioxide and the preparation of products are completed by a one-step method. The process comprises the following steps:
(1) the gas to be treated enters the tube side or the shell side of the hollow fiber membrane component through a flue gas dedusting and cooling system and a compressor or a blower and a gas flow control system;
(2) the alkali solution enters a hollow fiber membrane module tube side or shell side through an alkali solution filtering system and a cooling system by an alkali solution pump through a flow regulating system to be absorbed by carbon dioxide;
(3) carbon dioxide in the gas reacts with the alkali solution through the surface micropores of the hollow fiber membrane to capture the dioxide in the gas; wherein, the gas flow regulating system, the gas pressure control and alkali solution flow regulating system and the alkali solution pressure regulating system are used for maintaining a certain pressure difference between gas phase and liquid phase for absorption, and the pressure difference is between 0.05 and 0.25 MPa; the gas phase and the liquid phase are respectively arranged at the inner side and the outer side of the hollow fiber membrane, and are not in direct contact, so that the capture of carbon dioxide in the gas is realized;
(4) and collecting the absorbed alkali solution, and enabling the alkali solution to come out of the membrane absorber and enter a product preparation device.
2. The process as set forth in claim 1, wherein said basic solution is selected from the group consisting of NaOH and NH4OH。
3. The process method as claimed in claim 1, wherein the hollow fiber membrane material is hydrophobic membrane material, and polypropylene or polytetrafluoroethylene or polyvinylidene fluoride is selected; the micro-pore diameter of the fiber membrane is 0.02-2 μm; the porosity is 30-50%, and the film loading is 30-60%.
4. The process of claim 1 wherein the product preparation unit is a packed column.
CN202110813728.6A 2021-07-19 2021-07-19 For CO2Membrane absorption method for trapping and utilization Pending CN113521970A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115957730A (en) * 2023-01-04 2023-04-14 苏州西热节能环保技术有限公司 Preparation method of plate-type material for air direct carbon capture
CN116036826A (en) * 2023-04-03 2023-05-02 中国电力工程顾问集团有限公司 Carbon dioxide capturing system and method
WO2024002310A1 (en) * 2022-06-30 2024-01-04 中国石油天然气集团有限公司 Method for coupling carbon dioxide capture and hydrogen production, and system therefor
CN117339351A (en) * 2023-12-04 2024-01-05 广州佰宏新能源科技股份有限公司 Low-energy-consumption carbon dioxide capturing device and method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002028432A (en) * 2000-07-13 2002-01-29 Kobe Steel Ltd Pretreating device for air separating device
CN1488422A (en) * 2003-07-30 2004-04-14 浙江大学 Method and system for separating carbon dioxide form fume by hollow film membrane contactor
CN102228772A (en) * 2011-07-11 2011-11-02 中国石油化工集团公司 Process method for capturing carbon dioxide in flue gas through membrane absorption of amino solution
CN103120886A (en) * 2013-01-25 2013-05-29 重庆大学 Method for efficiently removing CO2 from flue gas with utilization of hollow fiber hydrophobic membrane
CN107866137A (en) * 2016-09-28 2018-04-03 中国石油化工股份有限公司 A kind of capture method of carbon dioxide in flue gas
CN109310951A (en) * 2016-03-25 2019-02-05 蓝色星球有限公司 Carbon dioxide (the CO that ammonia mediates2) method of seal and system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002028432A (en) * 2000-07-13 2002-01-29 Kobe Steel Ltd Pretreating device for air separating device
CN1488422A (en) * 2003-07-30 2004-04-14 浙江大学 Method and system for separating carbon dioxide form fume by hollow film membrane contactor
CN102228772A (en) * 2011-07-11 2011-11-02 中国石油化工集团公司 Process method for capturing carbon dioxide in flue gas through membrane absorption of amino solution
CN103120886A (en) * 2013-01-25 2013-05-29 重庆大学 Method for efficiently removing CO2 from flue gas with utilization of hollow fiber hydrophobic membrane
CN109310951A (en) * 2016-03-25 2019-02-05 蓝色星球有限公司 Carbon dioxide (the CO that ammonia mediates2) method of seal and system
CN107866137A (en) * 2016-09-28 2018-04-03 中国石油化工股份有限公司 A kind of capture method of carbon dioxide in flue gas

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024002310A1 (en) * 2022-06-30 2024-01-04 中国石油天然气集团有限公司 Method for coupling carbon dioxide capture and hydrogen production, and system therefor
CN115957730A (en) * 2023-01-04 2023-04-14 苏州西热节能环保技术有限公司 Preparation method of plate-type material for air direct carbon capture
CN116036826A (en) * 2023-04-03 2023-05-02 中国电力工程顾问集团有限公司 Carbon dioxide capturing system and method
CN117339351A (en) * 2023-12-04 2024-01-05 广州佰宏新能源科技股份有限公司 Low-energy-consumption carbon dioxide capturing device and method

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