CN110813087A - 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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- B01D53/34—Chemical or biological purification of waste gases
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention discloses a method and a system for treating high-concentration VOCs waste gas, which comprises the following steps: introducing high-concentration VOCs waste gas into a soluble organic matter absorption system, absorbing soluble VOCs, and collecting insoluble VOCs gas; introducing the wastewater absorbed with the soluble VOCs into a Fenton sludge circulating system for degradation; introducing the wastewater treated by the Fenton system into an MBR membrane sewage treatment system for treatment; degrading the collected insoluble VOCs gas through a photocatalytic system; and introducing the gas treated by the photocatalytic 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 which is difficult to treat is converted into the organic waste water which is easy to treat, the residual organic components which are difficult to dissolve in water are treated by photocatalytic degradation and activated carbon adsorption, so that the high-concentration VOCs waste gas is completely treated, the effluent gas reaches the discharge 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) mainly comprise fluorine-containing aromatic hydrocarbon, alcohol, ether and ester, and also comprise partial HCl and H2S and other inorganic substances have the characteristics of large concentration, complex components and strong toxicity.
At present, the treatment of VOCs mainly comprises a combustion method, an adsorption method and a catalysis method, wherein the combustion method is to directly introduce VOCs into an incinerator for combustion and convert the VOCs into CO2And H2And O. The method has simple operation and high treatment efficiency. But the equipment investment is high, and when other inorganic pollutants such as sulfide, nitrogen oxide and the like exist in VOCs, SO is generated after combustion2、NOXAnd the like, leading to secondary pollution of air. The adsorption method is to make VOCs pass through adsorbing materials such as active carbon, resin and the like, and adsorb pollutants in the adsorbing materials in pores, thereby achieving the purpose of purifying air. The method has the advantages of low investment and simple operation, and can remove inorganic pollutants, but the adsorption capacity and the adsorption efficiency of the resin are limited, so the method is not suitable for treating high-concentration VOCs. The catalysis method is to degrade pollutants into CO by passing VOCs through a catalyst and matching with an ultraviolet lamp2And H2And compared with combustion and adsorption, the treatment efficiency is high, and the tail gas can be efficiently degraded aiming at VOCs with high concentration and complex components, including various inorganic pollutants, so that the tail gas can reach the emission standard. However, this process requires a large investment in equipment and the catalyst needs to be replaced frequently, making it more expensive to operate.
In view of the defects of the above methods, technologies for treating VOCs by using a Fenton method have appeared at present, which can effectively oxidize organic substances in wastewater, but can only oxidize substances completely dissolved in water, but high-concentration VOCs usually contain a large amount of water-soluble VOCs and also contain a small amount of insoluble organic components, and the emission requirements can not be met by only using the Fenton method for treatment.
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 VOCs and reduce the treatment cost.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a method of treating an exhaust gas having a high concentration of VOCs, comprising the steps of:
A) absorbing water-soluble VOCs: introducing the high-concentration VOCs waste gas into a soluble organic matter absorption system, absorbing soluble VOCs gas, and collecting insoluble VOCs gas;
B) fenton oxidation: introducing the wastewater after absorbing the soluble VOCs gas into a Fenton sludge circulating system for degradation;
C) MBR treatment: introducing the wastewater treated by the Fenton sludge circulating system into an MBR membrane sewage treatment system for treatment;
D) photocatalytic degradation: degrading the collected insoluble VOCs gas through a photocatalytic system;
E) activated carbon adsorption treatment: and introducing the gas treated by the photocatalytic system into an activated carbon adsorption system for treatment.
Preferably, the concentration of the VOCs in the high-concentration VOCs waste gas is 3000-5000 mg/L.
Preferably, the pH value in the Fenton sludge circulating system is controlled to be 2.6-2.9, n (Fe)2+)：n(H2O2) 2.15-2.6, the reaction temperature is 30-35 ℃, and the reaction time is 30-50 min.
Preferably, a plate-type photocatalyst is arranged in the photocatalytic system, and the main component of the plate-type photocatalyst is TiO2。
Preferably, the electrolytic reaction is performed simultaneously in the Fenton oxidation step.
Preferably, the electrolysis conditions are: voltage is 20-30V, current is 1-5A, reaction temperature is 30-45 deg.C, reaction time is 20-40min, and pH value is controlled at 0.7-0.8.
More preferably, the electrolysis conditions are: voltage 24V, current 4A, reaction temperature 40 ℃ and reaction time 30 min.
Preferably, an acid is added during the electrolysis to control the pH value between 0.7 and 0.8, and the acid is preferably sulfuric acid.
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 sequentially connected; the absorption system is also connected with a photocatalytic system, and the photocatalytic system is connected with an activated carbon adsorption system.
Furthermore, the soluble organic matter absorption system is a water tank or a water tank, and the high-concentration VOCs waste gas is introduced into the soluble organic matter absorption system firstly, so that most of soluble organic matters in the VOCs waste gas are dissolved in water, the high-concentration organic waste gas which is difficult to treat can be converted into the organic waste water which is easy to treat, and the treatment difficulty of the waste water can be reduced.
Furthermore, a sealed gas-collecting hood is arranged above the water tank or the water tank and is used for collecting part of insoluble VOCs in the high-concentration VOCs waste gas.
Furthermore, the gas-collecting hood is connected with a photocatalytic system through a pipeline. The gas collecting hood can continuously exhaust gas to make the organic component which is difficult to dissolve in water and comes out from the water pool enter the photocatalytic system through the pipeline2. And the material of a connecting pipeline between the gas collecting hood and the photocatalytic system is U-PVC.
Further, in order to meet the emission requirement, the photocatalytic system is connected with an active carbon adsorption system through a connecting pipe of U-PVC; and the gas treated by the photocatalytic system enters an activated 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 directly discharged up to the standard.
Furthermore, the Fenton sludge circulating 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 the Fenton reaction begins to proceed, the electrolytic system is synchronously started, and Fe (OH) is generated3By the action of an electric current, converted into Fe2+Due to H2O2The addition amount of the catalyst is far larger than the reaction amount, so that the circulating Fenton reaction can be realized through electrolysis, and the addition amount of the reagent and the generation amount of sludge are greatly reduced.
Compared with the prior art, the invention has the following beneficial effects:
1) most of high-concentration VOCs waste gas is dissolved in water, high-concentration organic waste gas which is difficult to treat is converted into organic waste water which is easy to treat, and then Fenton oxidation degradation and membrane separation treatment are carried out, so that the treatment difficulty is reduced, and the effluent reaches the discharge standard; and the other part of organic components which are difficult to dissolve in water are treated by adopting photocatalysis degradation and activated carbon adsorption, so that the discharged gas reaches the emission standard. Through the synergistic effect of the steps of biological oxidation, membrane biological separation, photocatalytic degradation and activated 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 circulating system is provided with the electrolytic system, and the electrolytic system is started while the Fenton oxidation reaction is carried out, so that the organic matter degradation can be promoted, and the generated Fe can be generated3+Reduction to Fe by electrolysis2+Thereby reducing the dosage of the ferric salt, ensuring that the subsequent sludge yield can be obviously reduced, and the reduction rate of the ferric salt is more than 98 percent.
Drawings
FIG. 1 is a schematic diagram of a processing system architecture;
FIG. 2 is a schematic view of a process for treating waste gas containing high concentrations of VOCs.
In the figure, a dissolved organic matter absorption system 1; a Fenton sludge circulating system 2; an MBR membrane sewage treatment system 3; a photocatalytic system 4; an activated carbon adsorption system 5.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments of examples. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Embodiment one, system for handle high concentration VOCs waste gas
As shown in fig. 1, the system for treating high-concentration VOCs waste gas of the present invention comprises a dissolved organic matter absorption system, a Fenton sludge circulation system, and an MBR membrane sewage treatment system, which are connected in sequence through a pipeline.
In this 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 a U-PVC pipeline.
A sealed gas-collecting hood (not shown in the figure) is arranged above the water pool, the gas-collecting hood is connected with a photocatalytic system 4 through a pipeline, and insoluble VOCs gas which is one of products from the water pool can be sent into the photocatalytic system through the pipeline by continuously pumping; the connecting pipeline between the gas-collecting hood and the photocatalytic system is made of U-PVC.
The photocatalytic system is connected with an activated carbon adsorption system 5. Wherein the photocatalytic 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 the irradiation of the ultraviolet lamps2And discharged from the rear end. In order to increase the catalytic efficiency, the system is provided with a plate catalyst, the main component of which is TiO2. Through the U-PVC connecting pipe, the gas treated by the photocatalytic 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 is ensured to be directly discharged up to the standard.
The Fenton sludge circulating system is a conventional Fenton sludge circulating system and generally comprises a plurality of pipes which are sequentially connected with one another through pipelinesFenton oxidation tower, a neutralization tank, a degassing tank, a coagulation reaction tank and a final sedimentation tank (not shown in the figure). Wherein the bottom of the reaction tank of the oxidation tower is provided with an electrolysis system, when the Fenton reaction starts to be carried out, the electrolysis system is synchronously started, and the generated Fe (OH) is generated under the action of electrolysis3By the action of an electric current, converted into Fe2+Due to H2O2The addition amount of the catalyst is far larger than the reaction amount, so that the circulating Fenton reaction can be realized through electrolysis, and the addition amount of the reagent and the generation amount of the sewage and sludge are greatly reduced.
Example II method for treating waste gas containing high-concentration VOCs
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 water pool, dissolving most soluble organic matters into water, after absorption is finished, wherein the COD concentration in the water is approximately equal to 3000mg/L, and collecting insoluble VOCs gas, wherein the COD concentration in the gas is approximately equal to 12000 mg/L;
step 2, Fenton oxidation: introducing the wastewater absorbed with soluble VOCs into a Fenton sludge circulation system for degradation, wherein the pH value is approximately equal to 2.6-2.9, n (Fe) in the system2+)：n(H2O2) The reaction temperature T is approximately equal to 2.15 ℃, the reaction time T is approximately equal to 40 min; after the reaction is finished, the COD value in the wastewater is reduced from 4000mg/L to 720 mg/L; the electrolysis system is synchronously started to carry out electrolysis when the oxidation reaction starts, the voltage U is 24V, the current I is 4A, the reaction temperature T is approximately equal to 40 ℃, the reaction time T is 30min, and in order to ensure Fe (OH)3Can be reduced to Fe2+Adding a proper amount of 1.5mol/L sulfuric acid, and adjusting the pH value to 0.7-0.8; after the electrolysis is finished, the COD value in the wastewater is further reduced to 180mg/L from 720mg/L, and meanwhile, the reduction rate of the 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, after the electrolysis is finished, the effluent is treated by a membrane bioreactor for 3 hours, and the COD of the effluent can reach 25-32mg/L after the treatment is finished, so that the effluent reaches the discharge standard.
Step 4, photocatalytic degradation: degrading the collected insoluble VOCs gas by a photocatalysis system, wherein 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 additionally provided with a plate type catalyst, the main component of which is TiO2. After the treatment by the method, the concentration of the VOCs is reduced to 30mg/L from 1200 mg/L;
and 5, activated carbon adsorption treatment: and introducing the gas treated by the photocatalytic system into an activated carbon adsorption system to further adsorb residual VOCs, wherein the particle size of the activated carbon in the system is about 80 meshes, the adsorption time is 30min, and the concentration of the VOCs is further reduced to 0.2-0.4mg/L, so that the emission standard is reached.
Example III method for treating high-concentration VOCs waste gas
The difference between the third example and the second example is that the plate catalyst is V2O5/TiO2And the other parameters are the same as those in the embodiment, and the concentration of the VOCs in the wastewater is reduced from 1200mg/L to 30mg/L after the wastewater is treated by the method.
Example four method for treating high-concentration VOCs waste gas
Example four differs from example two in that the plate catalyst is V2O5/Al2O3The power of an ultraviolet lamp is 25W, the irradiation time is 30min, the other parameters are the same as those in the example 2, and the concentration of VOCs in the wastewater is reduced from 1200mg/L to 20mg/L after the wastewater is treated by the method.
Example five method for treating high concentration VOCs waste gas
The difference between the fifth and the second example is that the plate catalyst is V2O5-WO3/TiO2The power of an ultraviolet lamp is 15W, the irradiation time is 45min, the other parameters are the same as those in the example 2, and the concentration of VOCs in the wastewater is reduced from 1200mg/L to 12mg/L after the wastewater is treated by the method.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method of treating an exhaust gas containing high concentrations of VOCs, comprising the steps of:
A) absorbing water-soluble VOCs: introducing the high-concentration VOCs waste gas into a soluble organic matter absorption system, absorbing soluble VOCs gas, and collecting insoluble VOCs gas;
B) fenton oxidation: introducing the wastewater after absorbing the soluble VOCs gas into a Fenton sludge circulating system for degradation;
C) MBR treatment: introducing the wastewater treated by the Fenton sludge circulating system into an MBR membrane sewage treatment system for treatment;
D) photocatalytic degradation: degrading the collected insoluble VOCs gas through a photocatalytic system;
E) activated carbon adsorption treatment: and introducing the gas treated by the photocatalytic system into an activated carbon adsorption system for treatment.
2. The method as claimed in claim 1, wherein the concentration of VOCs in the high concentration VOCs waste gas is 3000-5000 mg/L.
3. The method of claim 1, wherein the pH of the Fenton sludge circulation system is controlled to 2.6-2.9, n (Fe)2+)：n(H2O2) 2.15-2.6, the reaction temperature is 30-35 ℃, and the reaction time is 30-50 min.
4. The method of claim 1, wherein a plate-type photocatalyst is disposed in the photocatalytic system, and the plate-type photocatalyst has TiO as a main component2。
5. The method of any one of claims 1 to 4, wherein the Fenton oxidation step is performed simultaneously with the electrolysis reaction.
6. The method of claim 5, wherein the electrolysis conditions are: voltage is 20-30V, current is 1-5A, reaction temperature is 30-45 ℃, and reaction time is 20-40 min.
7. The method of claim 6, wherein the electrolysis conditions are: voltage 24V, current 4A, reaction temperature 40 ℃ and reaction time 30 min.
8. The method of claim 6 or 7, wherein the pH is controlled to 0.7-0.8 by adding an acid during the electrolysis.
9. A system for treating high-concentration VOCs waste gas is characterized by comprising a soluble organic matter absorption system, a Fenton sludge circulation system and an MBR membrane sewage treatment system which are sequentially connected through pipelines; the soluble organic matter absorption system is also connected with a photocatalytic system, and the photocatalytic system is connected with an active carbon adsorption system.
10. The system of claim 9, further comprising an electrolysis system disposed at the bottom of the Fenton sludge recirculation system.
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