CN110813087B - Method and system for treating high-concentration VOCs waste gas - Google Patents
Method and system for treating high-concentration VOCs waste gas Download PDFInfo
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Classifications
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/14—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 absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C—CHEMISTRY; METALLURGY
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention discloses a method and a system for treating high-concentration VOCs waste gas, comprising the following steps: introducing the high-concentration VOCs waste gas into a soluble organic matter absorption system to absorb soluble VOCs and collect insoluble VOCs gas; introducing the wastewater after absorbing the soluble VOCs into a Fenton sludge circulation system for degradation; introducing wastewater treated by the Fenton system into an MBR membrane sewage treatment system for treatment; degrading the collected insoluble VOCs gas by a photocatalysis system; and introducing the gas treated by the photocatalysis system into an activated carbon adsorption system. According to the invention, most of the high-concentration VOCs waste gas is dissolved in water, the high-concentration organic waste gas difficult to treat is converted into the organic waste water easy to treat, the rest of the organic components difficult to dissolve in water are subjected to photocatalytic degradation and activated carbon adsorption treatment, so that the high-concentration VOCs waste gas is completely treated, the effluent gas reaches the emission standard, and the treatment difficulty and the treatment cost are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of pollutant treatment, and particularly relates to a method and a system for treating high-concentration VOCs waste gas.
Background
The volatile organic compounds (VOCs, volatile organic compounds) mainly comprise fluorine-containing aromatic hydrocarbon, alcohol, ether and esters, and further comprise part of HCl and H 2 S and other inorganic matters have the characteristics of large concentration, complex components and strong toxicity.
The prior treatment of VOCs mainly comprises a combustion method, an adsorption method and a catalytic method, wherein the combustion method is to directly introduce the VOCs into an incinerator for combustion, and then to carry out the combustionWhich is converted into CO 2 And H 2 O. The method is simple in operation and high in treatment efficiency. However, the investment in equipment is high, and when other inorganic pollutants such as sulfides, nitrogen oxides and the like exist in VOCs, SO is generated after combustion 2 、NO X And volatile pollutants, and causes secondary pollution of air. The adsorption method is to adsorb the pollutants in VOCs through adsorption materials such as active carbon, resin and the like in the pores of the adsorption materials, so as to achieve the aim of purifying air. The method has the advantages of low investment and simple operation, and can remove inorganic pollutants, but the adsorption quantity and adsorption efficiency of the resin are limited, so that the method is not suitable for treating high-concentration VOCs. The catalytic method is to make VOCs pass through the catalyst and simultaneously match with an ultraviolet lamp to degrade pollutants into CO 2 And H 2 Compared with combustion and adsorption, the O has high treatment efficiency, and can efficiently degrade various inorganic pollutants in VOCs with high concentration and complex components, thereby ensuring that the tail gas can reach the emission standard. However, this method is large in equipment investment and the catalyst needs to be replaced frequently, so that its running cost is higher.
Aiming at the defects of the method, a technology for treating VOCs by adopting a Fenton method is presented at present, the method can effectively oxidize organic substances in wastewater, but only can oxidize substances completely dissolved in water, but high-concentration VOCs usually contain most of water-soluble VOCs and also contain a small part of indissolvable organic components, and the emission requirement is still not met by the Fenton method alone.
Disclosure of Invention
The invention aims to provide a method and a system for treating high-concentration VOCs waste gas, which are suitable for treating high-concentration VOCs, improve the treatment effect of the VOCs and reduce the treatment cost.
In order to achieve the above object, the present invention adopts the following technical scheme: a method of treating high concentration VOCs off-gas comprising the steps of:
a) Absorption of water-soluble VOCs: introducing the high-concentration VOCs waste gas into a soluble organic matter absorption system, absorbing the soluble VOCs gas, and collecting insoluble VOCs gas;
b) Fenton oxidation: introducing the wastewater after absorbing the soluble VOCs gas into a Fenton sludge circulation system for degradation;
c) MBR treatment: introducing the wastewater treated by the Fenton sludge circulation system into an MBR membrane sewage treatment system for treatment;
d) Photocatalytic degradation: degrading the collected insoluble VOCs gas by a photocatalysis system;
e) And (3) activated carbon adsorption treatment: and introducing the gas treated by the photocatalysis system into an activated carbon adsorption system for treatment.
Preferably, the concentration of the high-concentration VOCs waste gas VOCs is 3000-5000mg/L.
Preferably, the pH value in the Fenton sludge circulation system is controlled to be 2.6-2.9, n (Fe) 2+ )：n(H 2 O 2 ) =2.15-2.6, reaction temperature 30-35 ℃, reaction time 30-50min.
Preferably, the photocatalytic system is provided with a plate-type photocatalyst, the main component of which is TiO 2 。
Preferably, the electrolytic reaction is performed simultaneously in the Fenton oxidation step.
Preferably, the electrolysis conditions are: the voltage is 20-30V, the current is 1-5A, the reaction temperature is 30-45 ℃, the reaction time is 20-40min, and the pH value is controlled to be 0.7-0.8.
More preferably, the electrolysis conditions are: the voltage is 24V, the current is 4A, the reaction temperature is 40 ℃, and the reaction time is 30min.
Preferably, an acid, preferably sulfuric acid, is added during the electrolysis to control the pH to 0.7-0.8.
The invention also provides a system for treating the high-concentration VOCs waste gas, which comprises a soluble organic matter absorption system, a Fenton sludge circulation system and an MBR membrane sewage treatment system which are connected in sequence; the absorption system is also connected with a photocatalysis system, and the photocatalysis system is connected with an activated carbon adsorption system.
Further, the soluble organic matter absorption system is a water tank or a water trough, and most soluble organic matters in the VOCs waste gas are dissolved in water by firstly introducing the high-concentration VOCs waste gas into the soluble organic matter absorption system, so that the high-concentration organic waste gas difficult to treat can be converted into the organic waste water easy to treat, and the treatment difficulty of the waste water can be reduced.
Further, a sealed gas collecting hood is arranged above the water tank or the water trough and is used for collecting part of insoluble Volatile Organic Compounds (VOCs) in the high-concentration VOCs waste gas.
Further, the gas collecting hood is connected with a photocatalysis system through a pipeline. The gas collecting hood can continuously exhaust air to enable organic components which are difficult to dissolve in water and come out of the water tank to enter the photocatalysis system through the pipeline, and in order to improve the catalysis efficiency, the system is also added with a plate-type catalyst, and the main component of the plate-type catalyst is TiO 2 . The connecting pipeline between the gas collecting hood and the photocatalysis system is made of U-PVC.
Further, in order to meet the emission requirement, the photocatalysis system is connected with an activated carbon adsorption system through a U-PVC connecting pipe; the gas treated by the photocatalysis system enters an active carbon adsorption system through a pipeline for further adsorption treatment. Furthermore, the activated carbon adsorption system is filled with 80-100 meshes of activated carbon, and residual tail gas is removed through the adsorption effect of the activated carbon, so that the discharged gas can be ensured to directly reach the emission standard.
Further, the Fenton sludge circulation system is an existing conventional system and generally comprises a Fenton oxidation tower, a neutralization tank, a degassing tank, a coagulation reaction tank and a final sedimentation tank which are sequentially connected through pipelines.
Further, an electrolysis system is arranged at the bottom of the Fenton sludge circulation system. When Fenton reaction starts to be carried out, the electrolysis system is synchronously started to generate Fe (OH) 3 Through the action of current, the Fe is converted into Fe 2+ Due to H 2 O 2 The adding amount of the catalyst is far larger than the reaction amount, so that the cyclic Fenton reaction can be realized through electrolysis, thereby greatly reducing the adding amount of the medicament and the generating amount of the sludge.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, most of the high-concentration VOCs waste gas is dissolved in water, and the organic waste gas which is difficult to treat is converted into the organic waste water which is easy to treat, and then Fenton oxidative degradation and membrane separation treatment are carried out, so that the treatment difficulty is reduced, and the effluent reaches the emission standard; and the other part of organic components which are difficult to dissolve in water are treated by adopting photocatalytic degradation and active carbon adsorption, so that the discharged gas reaches the emission standard. Through the synergistic effect of biological oxidation, membrane biological separation, photocatalytic degradation and active carbon adsorption, the complete treatment of the high-concentration VOCs waste gas is realized, and the treatment difficulty and the treatment cost are greatly reduced.
2) The bottom of the Fenton sludge circulation system is provided with the electrolysis system, and the electrolysis system is started while the Fenton oxidation reaction is carried out, so that not only can the degradation of organic matters be promoted, but also the generated Fe can be simultaneously generated 3+ Reduction to Fe by electrolysis 2+ Thereby reducing the adding amount of ferric salt, simultaneously ensuring that the subsequent sludge yield can be obviously reduced, and the reduction rate of ferric salt is more than 98 percent.
Drawings
FIG. 1 is a schematic diagram of a processing system;
fig. 2 is a schematic diagram of a process flow for treating high-concentration VOCs.
In the figure, a dissolved organic matter absorption system 1; a Fenton sludge circulation system 2; an MBR membrane sewage treatment system 3; a photocatalytic system 4; an activated carbon adsorption system 5.
Detailed Description
The above-described aspects of the present invention will be described in further detail by way of specific embodiments of the present invention. It should not be construed that the scope of the above subject matter of the present invention is limited to the following examples.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
Embodiment one, a system for treating high concentration VOCs exhaust gas
As shown in FIG. 1, the system for treating high-concentration VOCs waste gas comprises a soluble organic matter absorption system, a Fenton sludge circulation system and an MBR membrane sewage treatment system which are sequentially connected through pipelines.
In the embodiment, the soluble organic matter absorption system is a water tank 1, a water outlet of the water tank is communicated with a Fenton sludge circulation system 2 through a U-PVC pipeline, and the Fenton sludge circulation system is communicated with a conventional MBR membrane sewage treatment system 3 through the U-PVC pipeline.
A sealed gas collecting hood (not shown in the figure) is arranged above the water tank, the gas collecting hood is connected with a photocatalysis system 4 through a pipeline, and insoluble VOCs gas of the product from the water tank can be sent into the photocatalysis system through the pipeline by continuous air suction; the connecting pipeline between the gas collecting hood and the photocatalysis system is made of U-PVC.
The photocatalysis system is connected with an activated carbon adsorption system 5. Wherein the photocatalysis system is a transverse cylindrical reactor, 6-9 high-power ultraviolet lamps are fixed in the reactor, and gas enters from the front end of the reactor and is converted into CO through irradiation of ultraviolet light 2 And is discharged from the rear end. In order to improve the catalytic efficiency, the system is provided with a plate catalyst, the main component of which is TiO 2 . Through the U-PVC connecting pipe, the gas treated by the photocatalysis system enters an activated carbon adsorption system, 80-100 meshes of activated carbon is filled in the system, residual tail gas is removed through the adsorption effect of the activated carbon, and the discharged gas can be ensured to directly reach the emission standard.
The Fenton sludge circulation system is a conventional Fenton sludge circulation system, and generally comprises a Fenton oxidation tower, a neutralization tank, a degassing tank, a coagulation reaction tank and a final sedimentation tank (not shown in the figure) which are sequentially connected through pipelines. Wherein an electrolysis system is arranged at the bottom of the oxidation tower reaction tank, when Fenton reaction starts, the electrolysis system is synchronously started, and Fe (OH) is generated under the action of electrolysis 3 Through the action of current, the Fe is converted into Fe 2+ Due to H 2 O 2 The addition amount of the catalyst is far larger than the reaction amount, so that the cyclic Fenton reaction can be realized through electrolysis, thereby greatly reducing the addition amount of the medicament and the generation amount of sewage and sludge.
Embodiment II, a method for treating high-concentration VOCs waste gas
In this embodiment, the concentration of the high concentration VOCs waste gas is about 4000mg/L, and the specific treatment process is shown in FIG. 2.
Step 1, absorbing water-soluble VOCs: firstly, introducing high-concentration VOCs waste gas into a soluble organic matter absorption pond, dissolving most of soluble organic matters into water, and collecting insoluble VOCs gas with COD concentration of about 3000mg/L and COD concentration of about 12000mg/L in the water after the absorption is completed;
step 2, fenton oxidation: introducing the wastewater after absorbing the soluble VOCs into a Fenton sludge circulation system for degradation, wherein in the system, the pH is approximately equal to 2.6-2.9, and n (Fe 2+ )：n(H 2 O 2 ) The reaction temperature T is approximately equal to 2.15, the reaction time t=40 min, and the reaction temperature T is approximately equal to 32 ℃; the COD value in the wastewater after the reaction is finished is reduced from 4000mg/L to 720mg/L; the electrolysis system is synchronously started to electrolyze at the beginning of the oxidation reaction, the voltage U=24V, the current I=4A, the reaction temperature T approximately 40 ℃, and the reaction time t=30min are used for ensuring Fe (OH) 3 Can be reduced to Fe 2+ Adding proper amount of 1.5mol/L sulfuric acid, and adjusting the pH to 0.7-0.8; after the electrolysis is completed, the COD value in the wastewater is further reduced from 720mg/L to 180mg/L, and meanwhile, the reduction rate of ferric salt is more than 98 percent, so that the requirement of subsequent recycling can be basically met;
step 3, MBR treatment: in order to ensure that the effluent reaches the standard, the membrane bioreactor is adopted for treatment for 3 hours after the electrolysis is finished, and the COD of the effluent after the treatment can reach 25-32mg/L, thereby reaching the discharge standard.
Step 4, photocatalytic degradation: the collected insoluble VOCs gas is degraded by a photocatalysis system, the power of an ultraviolet lamp used by the system is 12W, the illumination time is 40min, and meanwhile, in order to improve the catalysis efficiency, the system is also added with a plate-type catalyst, and the main component of the catalyst is TiO 2 . After the treatment by the method, the concentration of the VOCs is reduced from 1200mg/L to 30mg/L;
step 5, activated carbon adsorption treatment: and introducing the gas treated by the photocatalysis system into an activated carbon adsorption system for further adsorbing residual VOCs, wherein the particle size of the activated carbon in the system is about 80 meshes, the adsorption time is 30min, the concentration of the VOCs is further reduced to 0.2-0.4mg/L, and the emission standard is reached.
Embodiment III, a method for treating high concentration VOCs exhaust gas
Embodiment III differs from embodiment II in that the plate catalyst is V 2 O 5 /TiO 2 The other parameters are the same as those of the embodiment, and the concentration of VOCs in the wastewater is reduced from 1200mg/L to 30mg/L after the wastewater is treated by the method.
Fourth embodiment, a method for treating high-concentration VOCs exhaust gas
The fourth embodiment differs from the second embodiment in that the plate catalyst is V 2 O 5 /Al 2 O 3 The power of the ultraviolet lamp is 25W, the irradiation time is 30min, the other parameters are the same as those of the example 2, and the concentration of VOCs in the wastewater is reduced from 1200mg/L to 20mg/L after the treatment by the method.
Fifth embodiment of the method for treating high-concentration VOCs waste gas
Embodiment five differs from embodiment two in that the plate catalyst is V 2 O 5 -WO 3 /TiO 2 The power of the ultraviolet lamp is 15W, the irradiation time is 45min, the other parameters are the same as those of the example 2, and the concentration of VOCs in the wastewater is reduced from 1200mg/L to 12mg/L after the treatment by the method.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Therefore, it is intended that all equivalent modifications and changes which a person having ordinary skill in the art can accomplish without departing from the spirit and technical spirit of the present invention shall be covered by the claims of the present invention.
Claims (6)
1. A method of treating high concentration VOCs off-gas comprising the steps of:
a) Absorption of water-soluble VOCs: introducing the high-concentration VOCs waste gas into a soluble organic matter absorption system, absorbing the soluble VOCs gas, and collecting insoluble VOCs gas;
b) Fenton oxidation: introducing the wastewater after absorbing the soluble VOCs gas into a Fenton sludge circulation system for degradation;
c) MBR treatment: introducing the wastewater treated by the Fenton sludge circulation system into an MBR membrane sewage treatment system for treatment;
d) Photocatalytic degradation: degrading the collected insoluble VOCs gas by a photocatalysis system;
e) And (3) activated carbon adsorption treatment: introducing the gas treated by the photocatalysis system into an activated carbon adsorption system for treatment;
in the Fenton sludge circulation system, n (Fe 2+ )：n(H 2 O 2 )＝2.15-2.6；
An electrolysis system is arranged at the bottom of the Fenton sludge circulation system, and electrolysis reaction is synchronously carried out in the Fenton oxidation step; and adding acid in the electrolysis process to control the pH value to be 0.7-0.8.
2. The method of claim 1, wherein the concentration of VOCs in the high concentration VOCs exhaust is 3000-5000mg/L.
3. The method according to claim 1, wherein the pH value in the Fenton sludge circulation system is controlled to be 2.6-2.9, the reaction temperature is 30-35 ℃, and the reaction time is 30-50min.
4. The method according to claim 1, wherein a plate-type photocatalyst is provided in the photocatalyst system, and the plate-type photocatalyst has a main component of TiO 2 。
5. The method of claim 1, wherein the electrolysis conditions are: the voltage is 20-30V, the current is 1-5A, the reaction temperature is 30-45 ℃, and the reaction time is 20-40min.
6. The method of claim 5, wherein the electrolysis conditions are: the voltage is 24V, the current is 4A, the reaction temperature is 40 ℃, and the reaction time is 30min.
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