CN111185089B - Novel technology for performing electro-Fenton catalytic degradation on VOCs - Google Patents

Novel technology for performing electro-Fenton catalytic degradation on VOCs Download PDF

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CN111185089B
CN111185089B CN202010023753.XA CN202010023753A CN111185089B CN 111185089 B CN111185089 B CN 111185089B CN 202010023753 A CN202010023753 A CN 202010023753A CN 111185089 B CN111185089 B CN 111185089B
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vocs
electro
catalytic degradation
fenton
solution
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CN111185089A (en
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江波
牛庆赫
刘树梁
孟宪哲
苏晴
关雨欣
宁亚男
王婧茹
刘奕捷
罗思义
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Qingdao University of Technology
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • 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
    • B01D53/38—Removing components of undefined structure
    • B01D53/44—Organic components
    • 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
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The invention relates to the field of atmospheric treatment, in particular to a novel electric heaterThe technology for catalytic degradation of VOCs. And introducing VOCs mixed gas into the solution from the bottom of the reactor through micropore aeration. In this system, anodic oxidation and cathodic catalysis produce H2O2The constructed Fenton reaction can generate a large amount of hydroxyl free radicals with strong oxidizing property, and the active species can oxidize VOCs aerated into a reaction system into soluble intermediate products, carbon dioxide, water, inorganic substances and other products. In addition, the aeration process of the VOCs can provide sufficient oxygen for cathode catalytic reduction, and H is promoted2O2The yield of (2). Utilize the elevator pump to promote the solution to reaction unit top, form the spraying through spray set, further increased the contact time and the area of contact of VOCs with the solution, promoted the treatment effeciency.

Description

Novel technology for performing electro-Fenton catalytic degradation on VOCs
Technical Field
The invention belongs to the application field of an atmosphere treatment technology, and particularly relates to a technology for catalyzing and degrading VOCs (volatile organic compounds) by utilizing electro-Fenton.
Background
Volatile Organic Compounds (VOCs) are organic compounds having a saturated vapor pressure of greater than 70.91Pa at normal temperature, a boiling point of 50-260 ℃ or lower at a standard atmospheric pressure of 101.3kPa and an initial boiling point of 250 ℃, or any organic solid or liquid that can be volatilized at normal temperature and pressure. Mainly include aliphatic hydrocarbons (e.g., cyclohexane and propylene), aromatic hydrocarbons (e.g., benzene and toluene), halogenated hydrocarbons (e.g., methylene chloride), alcohols (e.g., methanol and ethanol), aldehydes (e.g., formaldehyde and acetaldehyde), and ketones (e.g., acetone). VOCs play an important role in air pollution, can generate particulate matters PM2.5 and ozone, and are one of the main reasons for generating haze. In addition, most of the toxic VOCs directly harm human health, have adverse effects on human eyes and respiratory system, damage viscera and nervous system, and cause acute poisoning and even carcinogenesis in severe cases. Therefore, VOCs remediation has been a focus of research in recent years.
The technologies currently used for VOCs treatment include catalytic combustion, plasma, and microbial decontamination. The catalytic combustion method is characterized in that the discharged VOCs are combusted in a short time at a low temperature under the action of a specific catalyst and are finally converted into carbon dioxide and water. The technology does not produce open fire, has low combustion temperature and does not produce NOXHowever, the method has the disadvantages of catalyst poisoning, high energy consumption and the like. The plasma method technology is characterized in that high-energy electron rays are used for activating, ionizing and cracking each component of VOCs in exhaust gas, so that a series of complex chemical reactions such as oxidation and the like occur to degrade the VOCs, but the large-scale application of the VOCs is limited due to high energy consumption and high danger coefficient. The microbiological method is to convert volatile organic compounds into inorganic substances by using the metabolism of microorganisms, but can only treat low concentration of VOCs, and in addition, the technology has low treatment efficiency on organic gases with low solubility. Aiming at the technical defects in the field of VOCs treatment at present, a process method which is low in consumption and high in safety performance and solves the problem of VOCs is urgently needed.
Disclosure of Invention
In light of the above deficiencies of the prior art, the present invention provides a method for the catalytic degradation of VOCs using electro-Fenton.
The technical scheme of the invention is as follows: and introducing VOCs mixed gas into the solution from the bottom of the reactor through micropore aeration. In this system, anodic oxidation and cathodic catalysis produce H2O2The constructed Fenton reaction can generate a large amount of hydroxyl free radicals with strong oxidizing property, and the active species can oxidize VOCs aerated into a reaction system into soluble intermediate products, carbon dioxide, water, inorganic substances and other products. In addition, the aeration process of the VOCs can provide sufficient oxygen for cathode catalytic reduction, and H is promoted2O2The yield of (2). Using a lift pump to pump the electrolyteThe reaction device is lifted to the top of the reaction device, and spray is formed by the spraying device, so that the contact time and the contact area of the VOCs and the solution are further increased, and the treatment efficiency is improved.
Wherein, the preferred scheme is as follows:
the anode can be BDD electrode, DSA electrode, tin-antimony electrode, ruthenium-iridium electrode, iridium-tantalum electrode, PbO2Electrodes, and the like.
The cathode can be graphite, a carbon black/PTFE gas diffusion electrode, a graphite felt, a carbon felt loaded with carbon nanotubes and the like.
The electrode distance between the anode and the cathode can be 1-10 cm.
The current density can be 1-50mA/cm2And are not equal in between.
The pH value of the electro-Fenton system can be different from 2.0 to 6.0.
The concentration of the iron ions can be varied from 5 to 1000 mg/L.
The microporous aeration device can be a diaphragm type microporous aerator, a tubular aerator, a disc type aerator, a microporous ceramic aerator and the like.
The spraying device can be arranged at the top of the reactor, part of the electrolyte is lifted to the spraying device through the lifting pump to form spraying, and part of mixed gas overflowing the electrolyte is brought back to the system, so that the gas-liquid contact time and the contact area are increased. Further improving the degradation effect of the VOCs.
The invention has the advantages that:
(1) oxygen in the mixed gas of VOCs can be used as a raw material for cathode oxygen reduction reaction to generate a large amount of hydrogen peroxide and Fe added into the solution2+The reaction generates a strongly oxidizing hydroxyl radical (. OH).
(2) Part of VOCs is directly oxidized into H by utilizing a large amount of hydroxyl radicals (OH) with strong oxidizing property generated by the synergy of anodic oxidation and cathodic reduction2O and CO2。
(3) The technology operates at normal temperature and normal pressure, can be applied to the treatment of the VOCs at normal temperature and low concentration, and has no chemical reagent addition and no secondary pollution in the process.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
lead dioxide is used as an anode, and a carbon black/PTFE gas diffusion electrode is used as a cathode. Using 0.05M Na2SO4For the electrolyte, the initial pH was adjusted to 3 and a small amount of FeSO was added to the solution4. Chlorobenzene with a concentration of 200ppm was passed through a membrane microaeration chamber into solution at a flow rate of 1L/min. The electrolyte is sprayed from a spraying device at the top by a lift pump, and part of the gas overflowing from the solution is brought back into the solution again. The treated gas is connected with a gas chromatograph through a rubber tube at the top of the reactor, so that the treatment degree of the VOCs is monitored in real time.
The carbon black/PTFE gas diffusion electrode adopts a 20-mesh stainless steel net, forms mixed emulsion with absolute ethyl alcohol according to the mass ratio of the carbon black to the PTFE of 1:2, evaporates to remove the absolute ethyl alcohol, covers the paste on the stainless steel net, presses into a sheet by adopting proper pressure, and calcines for 60min at the high temperature of 350 ℃ in a muffle furnace.
The working current density is 20mA/cm2The oxidation absorption rate of VOCs is 96%.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.

Claims (7)

1. Process for electro-Fenton catalytic degradation of VOCsThe method is characterized in that: introducing VOCs mixed gas into the solution from the bottom of the reactor through micropore aeration; in this system, anodic oxidation and cathodic catalysis produce H2O2The constructed Fenton reaction can generate a large amount of hydroxyl free radicals with strong oxidizing property, and VOCs aerated into the reaction system can be oxidized into soluble intermediate products, carbon dioxide, water and inorganic matters by the active species; in addition, the aeration process of the VOCs can provide sufficient oxygen for cathode catalytic reduction, and H is promoted2O2The yield of (a); utilize the elevator pump to promote the solution to reaction unit top, form the spraying through spray set, further increased the contact time and the area of contact of VOCs with the solution, promoted the treatment effeciency.
2. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the anode is antimony-doped tin dioxide (Sb-SnO)2) Lead dioxide (PbO)2) Or Boron Doped Diamond (BDD).
3. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the cathode is graphite, a carbon black/PTFE gas diffusion electrode, a graphite felt and a carbon felt loaded with carbon nano tubes.
4. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the distance between the cathode and the anode is 1-10cm, and the current density is 1-50mA/cm2The input voltage waveform is direct current or pulse.
5. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the pH value of the electro-Fenton reaction is 2.0-6.0, and the concentration of iron ions is 5-1000 mg/L.
6. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the aeration device is a diaphragm type microporous aerator, a tubular aerator, a disc type aerator and a microporous ceramic aerator.
7. The process of claim 1, wherein the electro-Fenton catalytic degradation of VOCs comprises: the spraying device is arranged at the top of the reactor, and the electrolyte is lifted to the spraying device through the lifting pump to form spraying, so that part of overflowing VOCs is absorbed and degraded.
CN202010023753.XA 2020-01-09 2020-01-09 Novel technology for performing electro-Fenton catalytic degradation on VOCs Active CN111185089B (en)

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PCT/CN2020/075371 WO2021138959A1 (en) 2020-01-09 2020-02-14 Novel technology for catalytic degradation of vocs using electro-fenton

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CN114870616B (en) * 2022-06-10 2023-07-14 盐城工学院 electrobiological-Fenton-like integrated reactor for treating volatile organic waste gas
CN115318079A (en) * 2022-06-28 2022-11-11 中材国际环境工程（北京）有限公司 Gas treatment device and treatment method based on electrochemical technology
CN116462381B (en) * 2023-06-20 2023-09-01 生态环境部海河流域北海海域生态环境监督管理局生态环境监测与科学研究中心 Method for efficiently treating high-salt organic wastewater by using electro-Fenton and electro-Fenton-like technology
CN117531345B (en) * 2024-01-09 2024-04-19 天津大学 Electrochemical method for deodorizing, disinfecting and cleaning, and electrolytic cell device and system

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