CN106914127B - Method for treating nitrobenzene waste gas by coupling bacteria biological filter bed - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/00—Components to be removed
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Abstract
The invention relates to a coupling bacterium biological filter bed for processing nitrylThe benzene waste gas treating process includes setting polyurethane foam as stuffing, inoculating aerobic active sludge from nitrobenzene waste water treating plant, regulating the pH value of the nutritious liquid to 5.0 and constructing fungus-bacteria coupled biological filtering bed. Fungi can directly contact with nitrobenzene waste gas through hypha, and the problem that the mass transfer efficiency of hydrophobic VOCs in a traditional bacterial filter bed is not high is well solved. At the same time, based on the high biodiversity and mineralization capacity of bacteria, fungal metabolites can be further mineralized into carbon dioxide and water. When the concentration of nitrobenzene is 300-500mg m‑3When the method is used, the removal rate can reach 95-97 percent, and the removal load can reach 52.4-85.5g m‑3h‑1。
Description
Technical Field
The invention relates to the technical field of biological filtration for treating hydrophobic VOCs (volatile organic chemicals), in particular to a method for treating nitrobenzene waste gas by a coupling bacteria biological filter bed.
Background
VOCs are acronyms for volatile organic compounds (volatile organic compounds) and refer to the class of volatile organic compounds that are reactive. VOCs are harmful, such as benzene series, formaldehyde and the like, can cause cancers, and are also precursors of photochemical smog and can generate O3And secondary pollutants such as peroxyacetyl nitrate and the like play a vital role in generating haze. The 9-month academy of State of the government in 2013 issued "action plans for prevention and treatment of air pollution", ten items for atmosphere for short, wherein the promotion of volatile organic compound pollution control is explicitly pointed out. The atmospheric pollution control law newly revised 8 months in 2015 brings Volatile Organic Compounds (VOCs) into the supervision range for the first time. The petrochemical industry is one of the important sources of VOCs emission in China, and the emission amount of the VOCs emission source accounts for about 14.5% of the total emission amount of VOCs artificial sources. And the VOCs components discharged in the petrochemical industry are complex, contain hydrophilic VOCs and hydrophobic VOCs, are harmful greatly, and need to be treated urgently. In 12 months in 2014, the environmental protection department issues a comprehensive volatile organic compound remediation scheme in the petrochemical industry, the volatile organic compound remediation work in the petrochemical industry is developed first, and the total VOCs emission amount in the petrochemical industry is reduced by more than 30% in 2017.
Meanwhile, with the increasing enhancement of environmental awareness and the continuous health of environmental protection methods, the industrial unorganized discharge of VOCs is subject to strict legal constraints. Compared with other VOCs treatment technologies (such as adsorption technology, catalytic combustion technology, plasma technology and the like), the biotechnology is recognized as the most efficient, low-cost and environment-friendly technology for treating VOCs with low concentration and high air volume.
The traditional biological filter bed technology mainly utilizes bacteria to degrade hydrophilic VOCs, gas-phase pollutants are firstly dissolved in liquid-phase nutrient solution and then are connected with a biological membrane loaded on the surface of a filler, and then are adsorbed and metabolized by the bacteria and are converted into carbon dioxide, water and a new biological membrane, and the key process influencing the pollutant removal efficiency is the transfer of the pollutants from gas phase to liquid phase. However, the traditional biological filter bed has poor degradation effect due to the limitation of the mass transfer rate of the hydrophobic VOCs from the gas phase to the liquid phase.
The research of degrading VOCs waste gas by using a fungal biofilter bed is reported in the 1985 Science for the first time of reporting the degradation effect of white rot fungi Phanerochaete chrysosporium (hereinafter, P.chorososporium). The fungal reactor can well solve the problem of low mass transfer efficiency of hydrophobic VOCs (Henry constant >1) in a liquid phase. Fungi have an aerial hyphal structure and a large specific surface area, making it easier to adsorb contaminants from the gas phase. At the same time, fungi can tolerate extreme conditions of low pH and starvation compared to bacteria. However, the fungal reactor has the disadvantage that the start-up period of the fungal filter bed is relatively long due to the low metabolic rate of the fungal reactor compared to the aerobic bacterial biological filter bed. The fungus filter bed also has the defects of poor biological diversity, easy bacterial contamination and the like. In addition, because of its filamentous structure, the reaction is prone to clogging, and these factors limit the application of the fungal filter bed in the treatment of VOCs waste gases.
In summary, various problems exist in the treatment of the waste gas of the hydrophobic VOCs by the bacterial biofilter or the fungal biofilter, and the popularization and application of the biofiltration technology in the field of treating the hydrophobic VOCs are severely restricted.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for treating nitrobenzene waste gas by coupling a bacteria biofilter, which is used for eliminating low-concentration nitrobenzene in the waste gas by coupling the degradation capability of fungi and bacteria. The invention has the advantages of simple process equipment, convenient operation, high purification efficiency, low operation cost and no secondary pollution.
The technical scheme provided by the invention is as follows:
1) selecting filter bed fillers: selecting a polyurethane foam block with the side length of 4-6mm as a filler; filling a polyurethane foam block into a filler tower in a random stacking mode, wherein the porosity of the polyurethane foam block filler is 95%, the pore diameter is 0.8mm, and the bulk density is 0.015g cm-3Surface area of 1.7cm2cm-3Has a water-holding capacity of 55g-H2O g-1；
2) Preparing a nutrient solution: the nutrient solution contains 0.5g K per liter2HPO4、0.1g MgSO4·7H2O、4.5g KH2PO4、2gNH4Cl, 2mL of vitamin and trace mineral solution, and adjusting the pH value of the nutrient solution to 5.0;
3) inoculation of the biological filter bed: taking sludge in a secondary sedimentation tank of a sewage treatment plant of a nitrobenzene production enterprise as an inoculated strain, and carrying out dynamic domestication biofilm formation by adopting a gas-liquid circulation biofilm formation method; the concentration of the inoculated sludge is controlled to be 2000mg L-1Alternately spraying the mixed solution consisting of the sludge and the nutrient solution and the pure nutrient solution, wherein the spraying periods are 0.5h and 0.25h respectively, and the spraying amount is controlled to be 1.0L h-1；
4) Constructing a coupling bacterium biological filter bed: after the biofilm formation is finished, nutrient solution with the pH value of 5.0 is sprayed to the packing layer from top to bottom through a metering pump, the nutrient solution is sprayed for 2 hours every day, a coupling bacteria biofilter is constructed, and the adding amount of the nutrient solution is 174L m-3Polyurethane foam block filler d-1；
5) And (3) biological membrane characterization: the form of the biological membrane in the tower is observed through a Scanning Electron Microscope (SEM), and the construction completion of the fungus-bacterium coupling biological filter bed can be qualitatively judged from the form angle; the construction of the fungus-bacterium coupling biological filter bed can be quantitatively judged from the aspect of fungus and bacterium copy number through real-time fluorescent quantitative polymerase chain reaction (qPCR);
6) waste gas filtration: nitrobenzene waste gas enters from a gas distribution device at the bottom of the packed tower, the device is made of inert and elastic materials, a pipe orifice is flushed by airflow during gas inlet, and the pipe orifice is automatically closed during gas stop; the air inlet pipeline is provided with a check valve; the waste gas is in countercurrent contact with the nutrient solution sprayed from the top of the tower on the surface of the biological membrane.
In the packed tower, the temperature of the packing layer is controlled at 20-25 ℃. The polyurethane foam is selected as the filling layer, so that the polyurethane foam has the characteristics of biological inertia, strong physical and chemical stability, high porosity, strong water holding capacity, small head loss and the like, microorganisms are easy to attach to the surface of the filling layer, and the blocking period can be delayed.
The filler layer adopts polyurethane foam blocks with the side length of 4-6mm as fillers, which not only has larger surface area, but also can not cause compaction of the fillers after film hanging.
After the biofilm formation, the color of the biofilm on the surface of the filler can be obviously seen by naked eyes to be darker, and the air inlet concentration is 100 +/-10 mg m-3The concentration of the discharged gas is stabilized at 10mg m-3The success of the biofilm formation is indicated below.
The nutrient solution is uniformly sprayed on the surface of the biological membrane from the top of the tower through a nozzle, so as to provide nutrient elements and moisture for the growth of microorganisms. Meanwhile, the selective pressure of the pH value on microorganisms is utilized, the fungus copy number and the bacterium copy number in the biomembrane and the ratio of the fungus copy number to the bacterium copy number are artificially regulated, optimized and constructed in a mode of changing the pH value of the nutrient solution, the degradation performance of the fungus-bacterium coupling biological filter bed is coupled, and the removal capacity of the nitrobenzene waste gas is improved.
In step 6), the empty bed flow rate of nitrobenzene waste gas is controlled at 107.6m h-1The pressure drop is controlled to be 0-6cmH2And (4) an O column.
Preferably, the volume of the polyurethane foam block in the packed tower is 2.3L, the nutrient solution is sprayed for 2h every day, and the spraying amount is controlled to be 0.2Lh by a metering pump-1。
When the intake concentration of nitrobenzene is 300-500mg m-3Intake air rate of 107.6m h-1When the retention time is 20s, the removal rate is 95-97 percent, and the removal capacity can reach 52.4-85.5g m-3h-1。
Has the advantages that:
the invention takes polyurethane foam as a filler, takes aerobic activated sludge of a nitrobenzene wastewater treatment plant as an inoculated strain, adjusts the pH value of a nutrient solution to 5.0, and constructs a fungus-bacterium coupling biological filter bed to treat nitrobenzene waste gas. Fungi can directly contact with nitrobenzene waste gas through hypha, the problem that mass transfer efficiency of hydrophobic VOCs in a traditional bacterial filter bed is not high is well solved, and meanwhile, the fungal metabolites can be further mineralized into carbon dioxide and water based on high biological diversity and mineralization capacity of bacteria. When the concentration of nitrobenzene is 300-500mg m-3When the process is carried out, the removal rate can reach 95-97 percent, and the removal load can reach 52.4-85.5gm-3h-1。
The invention mainly aims at the problem that the capability of removing hydrophobic VOCs by the existing biological filtration technology is not strong, and applies the pH adjustment technology to artificially construct a fungus-bacterium coupling biological filter bed to couple the degradation capability of fungi and bacteria on the hydrophobic VOCs and improve the removal performance of the fungi and bacteria.
Drawings
FIG. 1: the process flow of the invention is schematically shown.
FIG. 2: example 1 biofilm characterization SEM images of fungal-bacterial coupled biofilter beds.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
Polyurethane foam blocks with the side length of 4-6mm are selected as fillers to construct the filler tower, so that the filler tower has a large surface area and cannot cause compaction after the fillers hang films; filling a polyurethane foam block into a filler tower in a random stacking mode, wherein the porosity of the polyurethane foam block filler is 95%, the pore diameter is 0.8mm, and the bulk density is 0.015g cm-3Surface area of 1.7cm2cm-3Has a water-holding capacity of 55g-H2O g-1(ii) a The temperature of the filler layer is controlled at 20-25 ℃.
Preparing a nutrient solution: each liter containing 0.5g K2HPO4、0.1g MgSO4·7H2O、4.5g KH2PO4、2g NH4Cl and 2mL vitamin and trace mineral solutionsThe pH value of the nutrient solution is adjusted to 5.0.
Taking sludge in a secondary sedimentation tank of a sewage treatment plant of a nitrobenzene production enterprise as an inoculated strain, and carrying out dynamic domestication biofilm formation by adopting a gas-liquid circulation biofilm formation method; the concentration of the inoculated sludge is controlled to be 2000mg L-1Alternately spraying the mixed solution consisting of the sludge and the nutrient solution and the pure nutrient solution, wherein the spraying periods are 0.5h and 0.25h respectively, and the spraying amount is controlled to be 1.0L h-1；
After inoculation, continuously spraying nutrient solution with pH value of 5.0 from top to bottom to the packing layer through a metering pump for 2h every day to construct a coupling bacteria biofilter, wherein the adding amount of the nutrient solution is 174Lm-3Polyurethane foam block filler d-1；
The biofilm was observed under an accelerating voltage of 15kV using a scanning electron microscope of Quanta 250FEG (FEI, USA). FIG. 2 is a representation of the biofilm of the fungal-bacterial coupled biofilter of example 1, and it is evident from the SEM images that a large number of filamentous fungi and partially globular fungi are interwoven. The measured data of the biofilm qPCR showed that the fungal copy number was 3.2X 106copies/. mu.L of bacteria at 1.8X 105copies/. mu.L. The qualitative analysis was consistent with the results of the quantitative determination.
Nitrobenzene waste gas enters from the bottom of the biological filter bed and is in countercurrent contact with nutrient solution sprayed from the top of the tower on the surface of the filler. The tower bottom is provided with a gas distribution device which is made of inert and elastic materials, the gas distribution pipe orifice is flushed by airflow when gas is supplied, and the gas distribution pipe orifice is automatically closed when the gas is stopped, so that the blockage can be avoided; the air inlet pipeline is provided with a check valve, so that the backflow of nutrient filtrate, waste gas and the like can be avoided.
When the intake concentration of nitrobenzene is 450mg m-3Intake air rate of 107.6m h-1The retention time is 20s, the removal rate is 95.3 percent, and the removal capacity can reach 77.2g m-3h-1。
Comparative example 1
The rest of the procedure was the same as in example 1. After the biofilm formation of the biological filter bed is successful, the pH value of the nutrient solution is kept to be 7.0, and when the air inlet concentration of nitrobenzene is 450mg m-3Intake air rate of 107.6m h-1Residence time of 20s, removal rate of 41.3%, removalCapacity 33.5g m-3h-1。
Although example 1 was operated under the same conditions as comparative example 1 except that the pH of the nutrient solution was different, the removal rate and the removal capacity of example 1 were 54% and 43.7g m higher than those of comparative example 1, respectively-3h-1. This is mainly because nitrobenzene is a typical hydrophobic VOCs, and its mass transfer efficiency in the conventional biological filter bed is low, which affects the degradation efficiency of the biological filter bed. In example 1, the pH of the nutrient solution was adjusted to 5.0, the original microbial community structure in the biofilm was changed, a fungal and bacterial coupled flora symbiotic at a certain population density and an optimal ratio was constructed, the degradation capacity of the two was coupled, and the removal performance of nitrobenzene waste gas by the biofilter was improved.
Example 2
The rest of the procedure was the same as in example 1. After the biofilm formation of the biological filter bed is successful, the pH value of the nutrient solution is adjusted to 5.0, and when the air inlet concentration of nitrobenzene is 400mg m-3Intake air rate of 107.6m h-1The residence time is 20s, the removal rate is 96 percent, and the removal capacity can reach 69.1g m-3h-1。
Example 3
The rest of the procedure was the same as in example 1. After the biofilm formation of the biological filter bed is successful, the pH value of the nutrient solution is adjusted to 5.0, and when the air inlet concentration of nitrobenzene is 350mg m-3Intake air rate of 107.6m h-1The retention time is 20s, the removal rate is 96.6 percent, and the removal capacity can reach 60.9g m-3h-1。
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (1)
1. A method for treating nitrobenzene waste gas by a coupling bacteria biofilter is characterized by comprising the following steps:
1) filter bedSelecting a filler: selecting a polyurethane foam block with the side length of 4-6mm as a filler, and filling the polyurethane foam block into a filler tower in a random manner, wherein the porosity of the polyurethane foam block is 95%, the pore diameter is 0.8mm, and the bulk density is 0.015 g-cm-3Surface area of 1.7cm2·cm-3Has a water-holding capacity of 55g-H2O·g-1；
2) Preparing a nutrient solution: the nutrient solution contains 0.5g K per liter2HPO4、0.1 g MgSO4·7H2O、4.5 g KH2PO4、2 gNH4Cl, 2mL of vitamin and trace mineral solution, and adjusting the pH value of the nutrient solution to 5.0;
3) inoculation of the biological filter bed: taking sludge in a secondary sedimentation tank of a sewage treatment plant of a nitrobenzene production enterprise as an inoculated strain, and carrying out dynamic domestication biofilm formation by adopting a gas-liquid circulation biofilm formation method; the concentration of the inoculated sludge is controlled to be 2000 mg.L-1Alternately spraying the mixed solution consisting of the sludge and the nutrient solution and the pure nutrient solution, wherein the spraying periods are 0.5h and 0.25h respectively, and the spraying amount is controlled to be 1.0 L.h-1；
4) Constructing a coupling bacterium biological filter bed: after the biofilm formation is finished, nutrient solution with the pH value of 5.0 is sprayed to the packing layer from top to bottom through a metering pump, the nutrient solution is sprayed for 2 hours every day, a coupling bacteria biofilter is constructed, and the adding amount of the nutrient solution is 174 L.m-3Polyurethane foam slabstock d-1；
5) And (3) biological membrane characterization: observing the form of a biological membrane in the tower through a scanning electron microscope SEM, and qualitatively judging the construction completion of the fungus-bacterium coupling biological filter bed from the form angle; quantitatively judging the construction completion of the fungus-bacterium coupling biological filter bed from the aspect of fungus and bacterium copy number through real-time fluorescent quantitative polymerase chain reaction (qPCR);
6) waste gas filtration: nitrobenzene waste gas enters from a gas distribution device at the bottom of the packed tower, the gas distribution device is made of inert and elastic materials, a pipe orifice is flushed by airflow during gas inlet, and the pipe orifice is automatically closed during gas stop; the air inlet pipeline is provided with a check valve; the waste gas is in countercurrent contact with the nutrient solution sprayed from the top of the tower on the surface of the biological membrane;
in the step 1), the temperature of the packing layer is controlled at 20-25 ℃;
in the step 3), the color of the biological film on the surface of the filler is obviously seen to be darker by naked eyes, and the air inlet concentration is 100 +/-10 mg.m-3The concentration of the discharged gas is stabilized at 10 mg.m-3Following, the sign of successful biofilm formation;
in the step 4), the polyurethane foam block is 2.3L, and the spraying amount is controlled to be 0.2 L.h by a metering pump-1；
In the step 6), the empty bed flow rate of the nitrobenzene waste gas is controlled at 107.6 m.h-1The pressure drop is controlled to be 0-6cm H2And (4) an O column.
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| CN108211699B (en) * | 2017-12-22 | 2021-09-21 | 江苏淮河化工有限公司 | Method for treating mononitrotoluene nitration tail gas |
| CN110237683B (en) * | 2019-05-27 | 2023-03-31 | 河北科技大学 | Enhanced absorption VOCs treatment device and method |
| CN113457359B (en) * | 2021-07-13 | 2022-09-06 | 中国矿业大学 | Device and method for treating organic waste gas by coupling ultraviolet light catalysis and microorganisms |
| CN115282766A (en) * | 2021-11-26 | 2022-11-04 | 山东建筑大学 | Biological trickling filtration method for purifying volatile organic compounds and synchronously generating electricity |
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| DE10003171C1 (en) * | 2000-01-25 | 2001-06-21 | Plasticon Kunststoff Gmbh | Gas purification, especially for desulfurizing and deodorizing waste gases, comprises passing a gas sequentially through beds of biologically active filter material having acidic and neutral pH values |
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