CN114053864A - Treatment method of waste gas containing organic pollutants - Google Patents
Treatment method of waste gas containing organic pollutants Download PDFInfo
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- CN114053864A CN114053864A CN202111532615.5A CN202111532615A CN114053864A CN 114053864 A CN114053864 A CN 114053864A CN 202111532615 A CN202111532615 A CN 202111532615A CN 114053864 A CN114053864 A CN 114053864A
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- 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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- 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
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention discloses a method for treating waste gas containing organic pollutants, and belongs to the technical field of waste gas treatment. The processing method comprises the following steps: 1) introducing the waste gas after filtering and removing particles into a slaked lime absorption tower to remove acidic pollutants contained in the waste gas; 2) introducing the gas treated in the step 1) into a spray tower, and spraying water mist containing lyase in the spray tower for removing organic pollutants contained in the waste gas; 3) demisting the gas discharged from the spray tower in the step 2), and introducing the gas into a biological filter; 4) and (3) treating the gas treated in the step 3) by a drying tower and then introducing the gas into an activated carbon absorption tower. According to the invention, the lyase is added into water and then sprayed out in a water mist manner, so that the water mist containing the lyase is fully mixed and contacted with the waste gas, and organic matters in the waste gas are more fully degraded.
Description
Technical Field
The invention belongs to the field of pollutant treatment, and particularly relates to a method for treating waste gas containing organic pollutants.
Background
In the sewage treatment process, a certain amount of harmful and odorous gas is usually generated, and certain influence is caused on a factory area and the surrounding environment. The harmful and odorous gas components generated in the sewage treatment process are different due to the sewage quality and the sewage treatment process. The organic wastewater contains gases containing Volatile Organic Compounds (VOC), and the boiling point of the VOC is 50-260 ℃ under normal pressure. The VOCs mainly comprise alkanes, aromatic hydrocarbons, alkenes, halocarbons, esters, aldehydes, ketones and the like, and comprise organic chlorides, Freon series, organic ketones, amines, alcohols, ethers, esters, acids, petroleum hydrocarbon compounds and the like. The VOCs waste gas is directly discharged into the atmosphere, which causes atmospheric pollution and harms human health.
For example, bisphenol A project sewage treatment plant for polycarbonate can generate peculiar smell in the operation process of sewage, because sulfate contained in organic waste water can be converted into sulfur ions under the condition of oxygen deficiency, and then malodorous gases such as hydrogen sulfide and the like are generated. The main components of the waste gas generated in sewage treatment are inorganic substances such as hydrogen sulfide and ammonia gas, organic substances such as aldehydes, methyl mercaptan, methyl sulfide, carbon disulfide and dimethyl disulfide, low-concentration volatile organic substances (organic acids) and the like, malodorous substances and the like, and the waste gas generated by facilities of a sewage station is required to be treated in order to protect the surrounding environment.
The existing method for treating the VOCs waste gas by adopting microorganisms is an environment-friendly and efficient method, but the microorganisms are directly adopted to treat the VOCs waste gas, and when the organic matters contained in the waste gas are various and have high toxicity, the method is not beneficial to the long-term stable operation of the biological filter. For example, chinese patent publication No. CN 112076622 a discloses a biofilter for treating exhaust gas and a method for treating exhaust gas thereof, wherein the method for treating exhaust gas comprises the following steps: step SS 01: a prewashing section, wherein the prewashing section comprises the following steps: step S011: waste gas firstly enters the biological filter tank through an air inlet above the prewashing tank and passes through the prewashing filler from top to bottom; step S012: the waste gas passes through the pre-washing filler from top to bottom and contacts with the biological liquid sprayed from top to bottom through a nozzle on the first circulating water pipe, and the temperature, the humidity and the pH value of waste gas pollutants are adjusted to the working condition suitable for the survival of microorganisms; step SS 02: the waste gas after passing through the prewashing section enters a biodegradation section, and the biodegradation section comprises the following steps: step S021: the waste gas passes through the biological filler from bottom to top; step S022: the waste gas passes through the biological filler from bottom to top and is in countercurrent contact with biological liquid sprayed from top to bottom through a nozzle on the circulating water pipe II, and pollutants in the waste gas are absorbed by microorganisms attached to the surface of the biological filler and are degraded into low-molecular harmless substances; step SS 03: and the gas passing through the prewashing section and the biodegradation section is discharged from the air outlet. The waste gas is biodegraded mainly through the biological filter, and although the waste gas is in countercurrent contact with biological liquid sprayed from top to bottom in both the prewashing section and the biodegradation section, the biological filter still has the problem that the biological filter is difficult to stably operate for a long time.
In addition, the prior art methods for treating exhaust gas containing organic pollutants still have the problem of poor pollutant removal effect due to low contact probability, which are all the problems to be solved by those skilled in the art.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the biological filter is difficult to stably operate for a long time caused by directly adopting the biological filter to treat waste gas and the pollutant removal effect is poor caused by low contact probability during the treatment of organic pollutants in the waste gas in the prior art, the invention provides the method for treating the waste gas containing the organic pollutants, wherein the waste gas is sprayed with water mist containing lyase before the biological filter, so that the contact efficiency of the lyase and the waste gas is increased; furthermore, the contact efficiency of organic pollutants in the waste gas and the filler of the biological filter is increased by introducing the waste gas into the biological filter in a gas distribution mode, so that the removal efficiency of the organic pollutants in the waste gas is improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for treating an exhaust gas containing organic pollutants, comprising:
1) introducing the waste gas after filtering and removing particles into a slaked lime absorption tower to remove acidic pollutants contained in the waste gas; since the lyase used in the next step is inactivated to a certain extent under a strong acidic condition, firstly, acidic pollutants in the waste gas are removed;
2) introducing the gas treated in the step 1) into a spray tower, and spraying water mist containing lyase in the spray tower for removing organic pollutants contained in the waste gas; the water mist containing the lyase increases the collision probability of the lyase and the organic pollutants in the waste gas, and the organic pollutants are more easily degraded by the lyase in the water mist;
3) demisting the gas discharged from the spray tower in the step 2), and introducing the gas into a biological filter;
4) and (3) treating the gas treated in the step 3) by a drying tower, and introducing the gas into an activated carbon absorption tower, wherein the activated carbon absorption tower is used as a last closing step for adsorbing residual organic pollutants which cannot be adsorbed in the previous step.
It is worth to be noted that, the biochemical action of the microorganism in the biological filter is utilized to decompose the pollutants and convert the pollutants into harmless or less harmful microorganisms, the organic matters are used as substrates required by the growth and the propagation of the microorganisms, the macromolecules or the organic matters with complex structures are finally oxidized and decomposed into simple inorganic matters such as water, carbon dioxide and the like through different conversion ways, and simultaneously, the organisms of the microorganisms are increased and propagated through assimilation and the energy generated in the process of the dissimilation, so that favorable conditions are created for further exerting the treatment capacity of the microorganisms on the organic matters; the waste gas contacts with water or water film on the surface of the biological filter packing, the pollutant is dissolved in the water to become molecules or ions in liquid phase, namely the pollutant is transferred from the gas phase to the liquid phase, and the process is a physical process and follows Henry's law:
Pi+＝HXi
in the formula, Pi is the equilibrium partial pressure of soluble gas in gas phase, MPa; h is a Henry coefficient, MPa; xi is the mole fraction of soluble gas in the liquid phase;
organic pollutant components in the water solution are adsorbed and absorbed by the microorganisms, and malodorous components are transferred from the water to the microorganisms; the water used as the absorbent is regenerated and recovered, and then is used for dissolving the pollutant components in the new waste gas; the organic matters adsorbed by the microorganisms are subjected to biotransformation, namely, the organic matters are sequentially taken into the body by the microorganisms after being dissolved by the extracellular enzymes of the microorganisms to insoluble and colloidal organic matters, and macromolecular organic matters such as starch, protein and the like are hydrolyzed into micromolecules under the action of the extracellular enzymes (hydrolytic enzymes) of the microorganisms and then enter the cell body; the malodor components entering the microbial cells are decomposed and utilized as energy or nutrients for the life activities of the microbes, thereby removing the contaminants.
Further, the lyase in the step 2) is laccase, and the activity unit of the laccase is 1-10 mu/g.
Further, the laccase in the step 2) is added into water in an amount of 2-10ppm, and more preferably 5-8 ppm.
Further, the temperature of the water mist containing the laccase in the step 2) is less than or equal to 80 ℃, and further preferably is 10-40 ℃; the pH value of the water mist containing the laccase is 4-8, and further preferably 6-7.5.
Further, defogging is handled including setting up ripple defogging layer at the spray column top layer in step 3), and defogging layer can effectual interception water smoke for gaseous moisture content descends, or sets up static mixer at the spray column gas outlet, and the waste gas that contains water smoke is through colliding in static mixer, makes the water smoke of catching organic pollutant separate from waste gas, effectively prevents organic pollutant along with the problem that waste gas flows, realizes gas-liquid separation.
Further, the liquid separated from the static mixer is returned to the aqueous solution added with the laccase again for spraying water mist containing the laccase in a spray tower. After a period of waste gas treatment, laccase is supplemented into the laccase water solution, so that the treatment efficiency of organic pollutants in the waste gas is ensured.
Further, an air distribution unit for shunting waste air is arranged in the biological filter.
Furthermore, a plurality of aeration heads are arranged on the air distribution unit, waste gas is introduced into the biological filter tank in an aeration mode and is introduced into the biological filter tank in an aeration mode, so that the waste gas can be fully contacted with fillers in the biological filter tank, and the removal efficiency of organic pollutants in the waste gas is improved.
Furthermore, a plurality of hollow membrane tubes are arranged on the air distribution unit, and the waste gas enters the biological filter through holes in the hollow membrane tubes.
Furthermore, the hollow membrane tube is made of enhanced polyvinylidene fluoride, the inner diameter of the hollow membrane tube is 1mm, and the outer diameter of the hollow membrane tube is 2 mm; the diameter of the pores is 0.1 to 0.5 μm.
It is worth explaining that the waste gas is introduced into the biological filter tank by adopting a hollow membrane tube mode, so that the waste gas can be more fully contacted with the filler in the biological filter tank, and the removal efficiency of the organic pollutants in the waste gas is further improved.
Furthermore, the waste gas contains one or more of phenol, toluene, xylene, quinones, acetone, methanol, ethanol, 1-propanol, hexanediol, 4-methyl-2-pentanol and methyl isobutyl ketone, styrene, benzene, ethylbenzene, cumene, isopropanol, isopropyl ether or n-pentane.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, the lyase is added into water and then sprayed out in a water mist manner, so that the water mist containing the lyase is fully mixed and contacted with the waste gas, and the organic matters in the waste gas are more fully degraded;
(2) the invention realizes the gas-liquid separation of water mist in the waste gas by arranging the demisting layer or the static mixer, and effectively avoids bringing organic pollutants absorbed in the water mist into the biological filter;
(3) the waste gas is further mixed with the water in the biological filter in an air distribution unit mode, for example, a plurality of aeration heads are arranged on the air distribution unit, the waste gas is introduced into the biological filter in an aeration mode and is introduced into the biological filter in an aeration mode, the waste gas can be fully contacted with the filler in the biological filter, and the removal efficiency of organic pollutants in the waste gas is improved; or a mode of arranging a plurality of hollow membrane pipes on the gas distribution unit can be adopted, so that the waste gas enters the biological filter through the holes on the hollow membrane pipes, the contact probability of the waste gas and the filler in the biological filter is increased, and the removal efficiency of organic pollutants in the waste gas is improved.
Drawings
FIG. 1 is a schematic view of a flow of exhaust gas treatment in example 1 of the present invention;
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all of the aforementioned values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
The invention is further described with reference to specific examples.
Example 1
Aiming at the waste gas containing the pollutants such as hydrogen sulfide, sulfur dioxide, methane, toluene, xylene and the like, wherein the content of each pollutant in the inlet gas is shown in table 1, the embodiment provides a method for treating the waste gas containing the organic pollutants, which comprises the following steps:
the method comprises the following steps of pretreatment, wherein firstly, the waste gas enters a belt type dust remover for dust removal under the action of a draught fan, and the purified waste gas is subjected to the following steps:
1) introducing the dedusted waste gas into an absorption tower filled with hydrated lime to remove acidic pollutants such as hydrogen sulfide, sulfur dioxide and the like in the waste gas;
2) laccase spray treatment:
the activity unit of the laccase adopted in the embodiment is about 10 ten thousand u/g, the addition amount of the laccase in water is 5ppm, a sprayer is arranged in a spray tower to spray out the water solution containing the laccase from top to bottom in a water mist mode, waste gas is introduced into the spray tower from the lower part of the spray tower, the water mist is in collision contact with the opposite gas, so that the pollutants in the waste gas are transferred to a liquid phase, and the transferred organic pollutants are recycled to the water solution containing the laccase along with the liquid; the treatment temperature of the step is 25 ℃, and the pH value of the aqueous solution containing the laccase is about 7;
the upper part of the spray tower is provided with a corrugated defogging layer which is used for intercepting water mist mixed in the waste gas so as to reduce the water content of the gas;
after a period of waste gas treatment, when the concentration of laccase in the laccase aqueous solution is reduced to be lower than 3ppm, laccase is supplemented to 5ppm in the laccase aqueous solution, so that the treatment efficiency of organic pollutants in the waste gas is ensured;
3) polyurethane filler is placed in the biological filter, the filling amount is 60%, before the biological filter is used, municipal sewage is adopted to carry out biofilm formation on the biological filter, the hydraulic retention time of the biofilm formation is 2 hours, and the biofilm formation stage lasts for 48 hours;
the bottom of the biological filter is provided with a plurality of aeration heads, and gas discharged by the corrugated demisting layer enters the biological filter through the aeration heads, so that the waste gas is fully contacted with the filler in the biological filter, and the removal efficiency of organic pollutants in the waste gas is improved;
4) treating the gas treated in the step 3) by a drying tower filled with molecular sieves, and introducing into an activated carbon absorption tower.
The contents of various organic pollutants in the exhaust gas from the activated carbon absorption tower are shown in table 1:
table 1 content of organic contaminants in inlet and outlet gases of example 1
In addition, the biofilter in the embodiment can still reach the outlet gas concentration of total hydrocarbon of 10mg/m after long-term stable operation for 180 days3The following.
Comparative example 1
Other conditions in the comparative example are the same as those in the example 1, the treated waste gas has the same source as that in the example 1, and the content of the components is slightly different, mainly the laccase spraying step in the step 2) is omitted, the gas passing through the slaked lime drying tower directly enters the biological filter in the step 3), and the content of pollutants in the discharged gas is shown in a table 2. Under the experimental conditions of the invention, the total hydrocarbon content of the gas discharged by directly adopting the biological filter to treat the waste gas reaches 140mg/m3Above, and after the biological filter tank is operated for 90 days, the outlet gas concentration of the total hydrocarbon is increased to about 200mg/m3The above.
Table 2 content of organic contaminants in inlet and outlet gas in comparative example 1
In comparison with comparative example 1, in the nearly same conditions, the waste gas is directly treated by the biofilter without laccase spray treatment, and the biofilter is difficult to stably operate for a long time.
Example 2
Aiming at the waste gas containing the pollutants such as hydrogen sulfide, methane, toluene, xylene and the like, wherein the content of each pollutant in the inlet gas is shown in table 3, the embodiment provides a method for treating the waste gas containing the organic pollutants, which comprises the following steps:
the method comprises the following steps of pretreatment, wherein firstly, the waste gas enters a belt type dust remover for dust removal under the action of a draught fan, and the purified waste gas is subjected to the following steps:
1) introducing the dedusted waste gas into an absorption tower filled with hydrated lime to remove acidic malodorous pollutants such as hydrogen sulfide and the like in the waste gas;
2) laccase spray treatment:
the activity unit of the laccase adopted in the embodiment is about 10 ten thousand u/g, the addition amount of the laccase in water is 10ppm, a sprayer is arranged in a spray tower to spray out the water solution containing the laccase from top to bottom in a water mist mode, waste gas is introduced into the spray tower from the lower part of the spray tower, the water mist is in collision contact with the opposite gas, so that the pollutants in the waste gas are transferred to a liquid phase, and the transferred organic pollutants are recycled to the water solution containing the laccase along with the liquid; the treatment temperature of the step is 25 ℃, and the pH value of the aqueous solution containing the laccase is about 6;
a static mixer is arranged at an air outlet at the upper part of the spray tower and is used for enabling waste gas mixed with water mist to collide in the static mixer, so that the water mist capturing organic pollutants is separated from the waste gas, the problem that the organic pollutants flow out along with the waste gas is effectively prevented, and gas-liquid separation is realized; returning the liquid separated from the static mixer to the aqueous solution added with the laccase again, and continuously spraying water mist containing the laccase in the spray tower; after a period of waste gas treatment, when the concentration of laccase in the laccase aqueous solution is reduced to be lower than 3ppm, laccase is supplemented to 10ppm in the laccase aqueous solution, so that the treatment efficiency of organic pollutants in the waste gas is ensured;
3) polyurethane filler is placed in the biological filter, the filling amount is 60%, before the biological filter is used, municipal sewage is adopted to carry out biofilm formation on the biological filter, the hydraulic retention time of the biofilm formation is 4 hours, and the biofilm formation stage lasts for 24 hours;
the bottom of the biological filter is provided with a plurality of hollow membrane tubes, the hollow membrane tubes are made of enhanced polyvinylidene fluoride, the inner diameter is 1mm, and the outer diameter is 2 mm; the diameter of the air hole is 0.2 μm; the gas discharged by the static mixer enters the biological filter through the hollow membrane tube, so that the waste gas is fully contacted with the filler in the biological filter, and the removal efficiency of organic pollutants in the waste gas is improved;
4) treating the gas treated in the step 3) by a drying tower filled with molecular sieves, and introducing into an activated carbon absorption tower.
The contents of various substances in the exhaust gas from the activated carbon absorption tower are shown in table 3:
table 3 content of organic contaminants in inlet and outlet gases of example 2
The biological filter in the embodiment can still reach the outlet gas concentration of total hydrocarbon of 8mg/m after long-term stable operation for 180 days3The following.
Example 3
The treatment method in this example was substantially the same as in example 2 except that the exhaust gas contained organic contaminants including hydrogen sulfide, methane, toluene, xylene, etc., in amounts shown in table 4.
Table 4 contaminant levels in the inlet and outlet gases of example 3
The biological filter in the embodiment can still reach the outlet gas concentration of total hydrocarbon of 15mg/m after long-term stable operation for 180 days3The following.
Example 4
The treatment method in this example was substantially the same as in example 2 except that the exhaust gas contained organic contaminants including hydrogen sulfide, methane, toluene, xylene, etc., in amounts shown in Table 5.
Table 5 contaminant content in inlet and outlet gases of example 4
The biological filter in the embodiment can still reach the outlet gas concentration of total hydrocarbon of 12mg/m after long-term stable operation for 180 days3The following.
The above description is illustrative of the present invention and its embodiments, and is not to be construed as limiting, and the embodiments shown in the examples are only one embodiment of the present invention, and the actual embodiments are not limited thereto. Therefore, if the person skilled in the art receives the teaching, the embodiment and the embodiment similar to the technical solution should be designed without creativity without departing from the spirit of the invention, and shall fall within the protection scope of the invention.
Claims (10)
1. A method for treating an exhaust gas containing organic pollutants, comprising:
1) introducing the waste gas after filtering and removing particles into a slaked lime absorption tower to remove acidic pollutants contained in the waste gas;
2) introducing the gas treated in the step 1) into a spray tower, and spraying water mist containing lyase in the spray tower for removing organic pollutants contained in the waste gas;
3) demisting the gas discharged from the spray tower in the step 2), and introducing the gas into a biological filter;
4) and (3) treating the gas treated in the step 3) by a drying tower and then introducing the gas into an activated carbon absorption tower.
2. The method for treating waste gas containing organic pollutants according to claim 1, wherein the lyase in the step 2) is laccase, and the activity unit of the laccase is 1-10 ten thousand u/g.
3. The method for treating waste gas containing organic pollutants according to claim 2, wherein the laccase is added in the water in the amount of 2-10ppm in step 2).
4. The method for treating the waste gas containing the organic pollutants according to claim 2, wherein the temperature of the laccase-containing water mist in the step 2) is not more than 80 ℃, and the pH of the laccase-containing water mist is 4-8.
5. The method for treating the waste gas containing the organic pollutants as claimed in claim 2, wherein the demisting treatment in the step 3) comprises arranging a corrugated demisting layer on the top layer of the spray tower, wherein the demisting layer can effectively intercept water mist, so that the water content of the gas is reduced, or arranging a static mixer at the gas outlet of the spray tower, so as to realize gas-liquid separation.
6. The method for treating the exhaust gas containing the organic pollutants according to any one of claims 2 to 5, wherein a gas distribution unit for shunting the exhaust gas is arranged in the biological filter.
7. The method according to claim 6, wherein the air distribution unit is provided with a plurality of aeration heads for introducing the exhaust gas into the biological filter by aeration.
8. The method according to claim 6, wherein the air distribution unit is provided with a plurality of hollow membrane tubes, and the waste gas enters the biological filter through holes on the hollow membrane tubes.
9. The method according to claim 8, wherein the hollow membrane tube is made of reinforced polyvinylidene fluoride, and has an inner diameter of 1mm and an outer diameter of 2 mm; the diameter of the pores is 0.1 to 0.5 μm.
10. The method for treating the exhaust gas containing organic pollutants as claimed in any one of claims 2 to 5, wherein the exhaust gas contains one or more of phenol, toluene, xylene, quinones, acetone, methanol, ethanol, 1-propanol, hexanediol, 4-methyl-2-pentanol, methyl isobutyl ketone, styrene, benzene, ethylbenzene, cumene, isopropanol, isopropyl ether or n-pentane.
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