CN110975539A - Liquid anode and application thereof in electromagnetic enhanced purification of toxic and harmful gases - Google Patents

Liquid anode and application thereof in electromagnetic enhanced purification of toxic and harmful gases Download PDF

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CN110975539A
CN110975539A CN201911169676.2A CN201911169676A CN110975539A CN 110975539 A CN110975539 A CN 110975539A CN 201911169676 A CN201911169676 A CN 201911169676A CN 110975539 A CN110975539 A CN 110975539A
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liquid
anode
ionic liquid
membrane
liquid anode
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CN110975539B (en
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瞿广飞
杨聪庆
李军燕
王芳
宁平
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/32Separation 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 electrical effects other than those provided for in group B01D61/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1456Removing acid components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1487Removing organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/406Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/408Cyanides, e.g. hydrogen cyanide (HCH)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708Volatile organic compounds V.O.C.'s
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/814Magnetic fields

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a liquid anode, which consists of ionic liquid, a porous membrane and a conductive electrode, wherein the ionic liquid is filled in a bag made of the porous membrane, and then the conductive electrode is placed in the ionic liquid to prepare the liquid anode; the liquid anode is applied to the electromagnetic strengthening purification of toxic and harmful gases, and the migration direction of gas molecules is changed under the action of two compound fields of an external electric field and a magnetic field, so that the gas molecules migrate to the liquid anode; the absorption performance of the electrode is improved under the drive of an electric field and a magnetic field, and the gas absorption rate is accelerated; the purification of the waste gas is realized; the electrode not only has the characteristics of high selectivity and high absorption capacity, but also has the characteristics of strong electrode designability, simple preparation, low energy consumption and recycling, and has engineering application prospect.

Description

Liquid anode and application thereof in electromagnetic enhanced purification of toxic and harmful gases
Technical Field
The invention belongs to the field of gas purification treatment, and particularly relates to a liquid anode and application thereof in electromagnetic enhanced purification of toxic and harmful gases.
Background
Toxic and harmful gases come from the aspects of life, industrial production and the like, deteriorate the living environment of people, cause great harm to human health and ecological environment, and have become a great environmental problem threatening the living development of human beings due to atmospheric pollution.
The technology for purifying the toxic and harmful gases comprises the following steps: adsorption, condensation, membrane separation, combustion, photodecomposition, plasma decomposition, ozone decomposition, and biological methods. The adsorption method has simple equipment, but has poor adsorption on the hydrocarbon waste gas, and most adsorption materials have short service life and are easy to cause secondary pollution; the condensation method has simple equipment and process, but has huge energy consumption during low-temperature condensation; the membrane separation method has simple flow and good separation effect, but the membrane material is expensive and has short service life; the combustion method has high process energy consumption and is easy to generate toxic and harmful substances; the biological method has low removal rate of the gaseous pollutants which are difficult to degrade. Therefore, the development of efficient, low-energy-consumption and low-cost gas separation and purification technology is one of the focus problems which are urgently needed to be solved at present.
In the patent "purification device for volatile organic compounds with liquid electrode" (publication number CN 205056226U), a liquid electrode is disclosed, which can make the discharge electrode plate of the purification device maintain the long-term discharge function, and is used for purifying organic compounds. The electrode is a water flow layer which is formed on the positive plate and continuously flows as a main body with a purifying effect, and the particles adsorbed by the positive plate are taken away by utilizing the scouring effect of the water flow layer, so that the aim of purification is fulfilled. The device has complicated and complicated gas purification process, single purification treatment object and low practicability; patent liquid electrode (publication number CN 105127000B) describes a liquid electrode for purifying oil smoke without cleaning and maintenance, which also takes the scouring action of water flow layer as the core, and the particles adsorbed on the electrode plate are carried away by the flow of the water flow layer. The electrode unit is complex in arrangement, and the electrode only plays a role in dust removal and has no purification effect on high-toxicity pollutants.
Disclosure of Invention
Aiming at the problem that toxic and harmful gases in industrial waste gas are difficult to purify, the invention provides the liquid anode which is simple to operate, large in absorption capacity, low in operation working voltage, recyclable, economical and efficient, and the enrichment and separation of high-toxicity pollutants are enhanced under the action of an applied electromagnetic composite field; the method comprises the following steps of coupling a conductive electrode, ionic liquid and a porous membrane to form a liquid anode, namely filling the ionic liquid into a bag made of the porous membrane, and then placing the conductive electrode into the ionic liquid to obtain a liquid anode material; the ionic liquid is uniformly filled in the porous membrane, the porous membrane not only plays a role of immobilizing the ionic liquid, but also has a high specific surface area, so that the contact chance of the waste gas to be treated and the ionic liquid is increased, and then the conductive electrode is placed in the center of the ionic liquid to prepare a liquid anode; when the device is used, an electric field is generated by connecting the conductive electrode of the liquid anode with an external power supply, and a magnetic field is generated by an external magnetic field generator.
The cation of the ionic liquid is one of guanidines, alcamines, imidazoles, pyridines, pyrazinium, pyrimidinium, quaternary ammonium salts, phosphonate and quaternary phosphonium salts, and the anion is [ BF ]4]-、[PF6]-、[NTf2]-、[Me]-、[DCA]-、[CF3CF2CF2COO]-、[CF3SO3]-、[C3F7COO]-、[C(CF3SO2)3)]-、[C4F9SO3]-、[(CF2SO2)N]-、[SbF6]-One of (1); the anion or cation of the ionic liquid is provided with an ether group, a carboxyl group, a hydroxyl group, an amino group, a cyano group, a naphthenic group or a cycloalkenyl group; the ionic liquid can be prepared by a conventional method according to a simple preparation method.
The porous membrane is one of a polyimide membrane, a polydimethylsiloxane membrane, a polysulfone hollow fiber membrane, a polyvinylidene chloride membrane and a polyacrylonitrile membrane; the membrane is provided with holes with the aperture of 0.5-15 mu m, and the thickness of the membrane is 0.1-0.15 mm; the porous membrane has the characteristics of stable structural property, high flux, high temperature resistance, large specific surface area, good ductility, strong pollution resistance and long service life.
The conductive electrode is one of a metal electrode or a non-metal electrode; the conductive electrode is externally connected with a power supply, and the voltage is 10-50V.
The other purpose of the invention is to apply the liquid anode in the electromagnetic strengthening purification of poisonous and harmful gas, and the poisonous and harmful gas is purified by 3-17m3The flow of/min is introduced into a container provided with a liquid anode and a liquid cathode, the liquid anode and the liquid cathode are connected with the anode and the cathode of a power supply at the temperature of 20-Treating toxic and harmful gas at 65 deg.C, magnetic field strength of 0.1-20T and voltage of 10-50V.
The toxic and harmful gas is VOCs and Nitrogen Oxide (NO)X) Sulfur oxide, cyanide, NH3And the like.
In order to improve the solubility of the toxic and harmful gas in the ionic liquid, the Henry's law ratio of 0.2-30bar is satisfied between the toxic and harmful gas and the ionic liquid.
The absorption and purification of the liquid anode to the gas is a mass transfer process. When the ion liquid is used, an electric field is generated by connecting the conductive electrode with an external power supply, and the magnetic strength is generated by an external magnetic field generator, so that gas molecules are transferred to the liquid anode under the action of a composite field. The high specific surface area and high porosity of the solid-supported membrane can enhance the contact interface of the ionic liquid and the gas, and the ionic liquid utilizes the specific hydrogen bond network structure and the special function of the functional group grafted by the anions and the cations and the gas to be treated to place the gas to be treated in the reticular gaps of the ionic liquid to be fixed, thereby realizing the absorption and purification of the toxic and harmful gas.
The invention has the advantages that:
the liquid anode has the advantages of low cost of raw materials, easy preparation, good stability, convenient operation, low energy consumption and good reliability; the electrode can be recycled, so that the gas purification effect is not influenced;
the liquid anode takes the porous structure of the porous membrane as a support, the electrode has good mechanical property, a sufficient area is provided for the contact of the ionic liquid and the gas, and compared with the common electrode material, the liquid anode has the advantages of large electrode porosity and specific surface area, large electrode absorption capacity and contribution to the diffusion and absorption of purified gas;
the liquid anode has strong designability, can introduce different functional groups according to the characteristics of different gases, realizes the functional requirements of absorption and purification of gases with different properties, has wider application range compared with the traditional gas absorption method, and breaks through the limitation of purifying gases by the traditional absorption method. Has certain reference significance for the research and development of new materials and new equipment in the field of air pollution.
Detailed Description
The present invention is further illustrated in detail by the following examples, but the present invention is not limited thereto.
Example 1: the CO concentration in certain industrial waste gas is 1000mg/m3,NOXThe concentration is 500mg/m3,SO2The concentration is 450mg/m3
The industrial waste gas is heated to 5m3Introducing into a closed reaction vessel at a flow rate of/min, wherein the ionic liquid of the liquid anode is 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide [ EMIM ]][Tf2N]The ionic liquid is prepared in accordance with "Raeisi S, Florusse L J, Peters C J. Purification of blue gas by ionic liquids: Carbonmoxide capture [ bmim][Tf2N][J]Aiche Journal, 2013, 59(10):3886-3891. "Hexafluorotetracarboxylic dianhydride type polyimide film as porous film material (pore size 10 μm, thickness 0.1 mm), and the porous film production method is referred to" Wang R, Cao Y, Vora R, et al, Fabrication of 6 FDA-Dual polyimide emulsion fibers for gas separation [ J]Journal of applied Polymer Science, 2001, 82(9): 2166-; the liquid anode conductive electrode is a Cu electrode; filling the ionic liquid into a bag made of a porous membrane, and then placing a Cu electrode into the ionic liquid to prepare a liquid anode;
the liquid anode, the Fe cathode and an external power supply are connected with a voltage of 25V and the magnetic field intensity of an external magnetic generator is 10T, industrial waste gas moves to the liquid anode under the action of a composite field at the temperature of 25 ℃ and under the pressure of 0.1MPa, and then penetrates through the aperture of the porous membrane to react with 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide [ EMIM ]][Tf2N]Fully contacting, treating CO and SO in the industrial waste gas for 3 hours2、NOXThe removal rates of the catalyst can reach 90%, 84.31% and 85.2% respectively.
Example 2: the concentration of dichloromethane in certain industrial waste gas is 800mg/m3
The industrial waste gas is treated by the method of 10m3The flow rate of the solution is/min, the solution is introduced into a closed reaction container, and the ionic liquid of the liquid anode is selected from [ BD ]][N5],[BD][N5]The preparation of ionic liquid refers to the application research of 'Wan' and the Min 'qi' and the ionic liquid method for absorbing chlorine-containing waste gas [ D]Beijing university of chemical industry, 2017 ", polysulfone hollow fiber membrane as porous membrane (pore size 5 μm, thickness 0.12 mm), porous membrane preparation is referred to as" Ismail AF, Dunkin IR, Gallivan S L, et al]Polymer, 1999, 40(23):6499-6506 ", the conductive electrode of the liquid anode was a Pt electrode, the ionic liquid was filled in the porous membrane bag, and then the Pt electrode was placed in the ionic liquid to prepare the liquid anode;
the liquid anode and the Cu cathode are externally connected with a power supply, the voltage is 20V, the magnetic field intensity of an external magnetic field generator is 15T, industrial waste gas can permeate through the porous membrane without hindrance under the action of a composite field and fully contact with ionic liquid under the conditions of 50 ℃ and 0.1MPa, and after the industrial waste dichloromethane is treated for 2 hours, the removal rate of the industrial waste dichloromethane reaches 93.45%; the temperature is increased, the viscosity of the ionic liquid is reduced, the mass transfer of the gas in the ionic liquid is accelerated, and the permeability of the gas is enhanced.
Example 3: the ethylene concentration in a certain waste gas is 800mg/m3Ethane concentration of 760 mg/m3
The exhaust gas has a particle size of 10m3The min flow is introduced into a closed reaction container, and the ionic liquid of the liquid anode adopts disubstituted functionalized ionic liquid [ (CP)2im][NTf2]The preparation of the ionic liquid refers to the application basic research of the ionic liquid in the separation of ethylene/ethane and 1-hexene/n-hexane [ D]Zhejiang university, 2012 "; the porous membrane is a polypropylene hollow fiber membrane (aperture 7 μm, thickness 0.15 mm), and the porous membrane preparation is referred to as "Peng J F, Liu J F, HuX L, et al]Journal of Chromatography A, 2007, 1139(2):165-170. "; the conductive electrode of the liquid anode is a Zn electrode, ionic liquid is filled in a bag made of the porous membrane, and then the Zn electrode is placed in the ionic liquid to prepare the liquid anode;
the liquid anode and the graphite electrode are externally connected with a power supply, the voltage is 20V, and the magnetic field intensity of an external magnetic generator is 10T under the conditions of 60 ℃ and 0.1 MPa; the waste gas moves to the liquid anode under the action of magnetic field force and electric field force, the reaction lasts for 4 hours, the ethylene removal rate reaches 96.4 percent, and only about 13 percent of ethane is absorbed, so that the selective separation of ethane/ethylene gas is realized. The ethane/ethylene gas separation rate reaches 87%.
Example 4: some waste gas mainly contains CH4、CO2、H2S and other harmful gases, and the industrial waste gas is treated by mixing with water at a pressure of 12m3The flow rate of the solution is/min, the solution is introduced into a closed reaction vessel, and the ionic liquid of the liquid anode is selected from [ pyr11][Tf2N]And [ pyr14][Tf2N]The mixtures and ionic liquids are prepared according to the references "Tom é, Liliana C, Mecerreyes D, free C S R, et al, Pyrrolidinium-based polymeric liquid materials: New spectra for CO2separation membranes[J]Journal of Membrane Science, 2013, 428: 260-; the porous membrane is polyvinylidene fluoride (with aperture of 8 μm and thickness of 0.12 mm), and the porous membrane is prepared according to Lee S H, Kim BS, Lee E W, et al]Desalinization, 2006, 200(1-3):21-22. "; filling the ionic liquid into a bag made of a porous membrane by using a Fe electrode as a conductive electrode, and then putting the Fe electrode into the ionic liquid to prepare a liquid anode;
connecting a liquid anode and a graphite electrode with an external power supply, connecting the external power supply with 25V at 50 ℃ and 0.1MPa, wherein the magnetic field intensity provided by an external magnetic field generator is 20T, the waste gas moves to the liquid anode under the action of magnetic field force and electric field force, and after reacting for 4H, H in the industrial waste gas2S removal rate reaches 94%, and CO removal rate reaches2The removal rate reaches 90 percent, and only 5 percent of CH is removed4The gas is absorbed, and the liquid anode pair H2S and CO2Has better osmotic absorption capacity and can selectively absorb CH4Separating; has good application prospect.

Claims (8)

1. A liquid anode, characterized by: the ionic liquid anode is composed of ionic liquid, a porous membrane and a conductive electrode, wherein the ionic liquid is filled in a bag made of the porous membrane, and then the conductive electrode is placed in the ionic liquid to prepare the liquid anode.
2. A liquid anode as claimed in claim 1, wherein: the cation of the ionic liquid is one of guanidines, alcamines, imidazoles, pyridines, pyrazinium, pyrimidinium, quaternary ammonium salts, phosphonate and quaternary phosphonium salt, and the anion is [ BF ]4]-、[PF6]-、[NTf2]-、[Me]-、[DCA]-、[CF3CF2CF2COO]-、[CF3SO3]-、[C3F7COO]-、[C(CF3SO2)3)]-、[C4F9SO3]-、[(CF2SO2)N]-、[SbF6]-One kind of (1).
3. A liquid anode as claimed in claim 2, wherein: the anion or cation of the ionic liquid is provided with an ether group, a carboxyl group, a hydroxyl group, an amino group, a cyano group, a naphthenic group or a cycloalkenyl group.
4. A liquid anode as claimed in claim 1, wherein: the porous membrane is one of polyimide membrane, polydimethylsiloxane membrane, polysulfone hollow fiber membrane, polyvinylidene chloride membrane and polyacrylonitrile membrane; the membrane is provided with pores with the pore diameter of 0.5-15 μm, and the thickness of the membrane is 0.1-0.15 mm.
5. A liquid anode as claimed in claim 1, wherein: the conductive electrode is a metal electrode or a non-metal electrode.
6. The use of the liquid anode of any one of claims 1 to 5 for the electromagnetic enhanced purification of noxious and harmful gases, wherein: the poisonous and harmful gas is heated to 3-17m3/minThe flow is introduced into a reaction container provided with a liquid anode and a liquid cathode, the liquid anode and the liquid cathode are connected with the anode and the cathode of a power supply, and toxic and harmful gases are treated at the temperature of 20-65 ℃, the magnetic field intensity of 0.1-20T and the voltage of 10-50V.
7. Use according to claim 6, characterized in that: the toxic and harmful gas contains VOCs, nitrogen oxides, sulfur oxides, cyanides and NH3One or more of them.
8. Use according to claim 6, characterized in that: the toxic and harmful gas and the ionic liquid meet Henry's law ratio of 0.2-30 bar.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111762853A (en) * 2020-06-19 2020-10-13 昆明理工大学 Liquid anode and method for enriching and separating anions in water body by using same
CN114748986A (en) * 2022-04-22 2022-07-15 昆明理工大学 Synchronous defluorination and denitration method for composite absorbent

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US20180265993A1 (en) * 2017-02-27 2018-09-20 Honeywell International Inc. Electrochemical carbon dioxide converter and liquid regenerator
CN108570686A (en) * 2017-03-07 2018-09-25 帕洛阿尔托研究中心公司 System and method for adjusting the gas concentration lwevel in internal ambience
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111762853A (en) * 2020-06-19 2020-10-13 昆明理工大学 Liquid anode and method for enriching and separating anions in water body by using same
CN114748986A (en) * 2022-04-22 2022-07-15 昆明理工大学 Synchronous defluorination and denitration method for composite absorbent
CN114748986B (en) * 2022-04-22 2024-05-10 昆明理工大学 Synchronous defluorination and denitration method for composite absorbent

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