WO2020156371A1 - 一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法 - Google Patents

一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法 Download PDF

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WO2020156371A1
WO2020156371A1 PCT/CN2020/073446 CN2020073446W WO2020156371A1 WO 2020156371 A1 WO2020156371 A1 WO 2020156371A1 CN 2020073446 W CN2020073446 W CN 2020073446W WO 2020156371 A1 WO2020156371 A1 WO 2020156371A1
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sulfur dioxide
exhaust gas
nitrogen oxides
packed tower
simultaneously removing
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PCT/CN2020/073446
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English (en)
French (fr)
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李侃
张徐祥
任洪强
孙佩石
张志超
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南京大学
南京大学宜兴环保研究院
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Publication of WO2020156371A1 publication Critical patent/WO2020156371A1/zh
Priority to US17/387,659 priority Critical patent/US20210354086A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B01D53/85—Biological processes with gas-solid contact
    • 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
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
    • 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
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/608—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/80—Organic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/124—Liquid reactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to the technical field of biological industrial waste gas purification, in particular to a method for simultaneously removing high-load sulfur dioxide and nitrogen oxides in waste gas.
  • Sulfur oxides SO X and nitrogen oxides NO X are the main air pollutants, which are emitted during the combustion of fossil fuels.
  • Nitrogen oxide NO X contains a variety of compounds, of which NO and NO 2 are the main pollutants, and they cause serious environmental problems due to their role in photochemical smog, acid rain and ozone depleting agents.
  • Sulfur dioxide SO 2 is the most important part of sulfur oxide SO X , accounting for more than 96%, so SO 2 can generally represent sulfur oxide.
  • SO 2 directly leads to the formation of acid rain and the loss of the ozone layer. As SO X and NO X emissions and environmental pollution have received increasing attention, the cleaning process of flue gas has attracted widespread attention.
  • the main obstacle in the traditional flue gas purification process is to treat solvents and solid adsorbents containing pollutants in an effective and environmentally friendly manner.
  • simply treating sulfur dioxide and nitrogen oxides as pollutants is not conducive to the reuse of sulfur and nitrogen resources and the realization of circular economy.
  • the flue gas containing SO X , NO X , CO 2 and other components can provide nutrients in the liquid or aerosol as a substrate for the growth of microorganisms.
  • Biological filters have become one of the most commonly used technologies in flue gas treatment due to their economical benefits, high efficiency at ambient temperature, no maintenance, long life, low operating costs and environmental friendliness.
  • biofilm packed tower flue gas simultaneous desulfurization and denitrification system uses a single biofilm packed tower flue gas simultaneous desulfurization and denitrification system, by adding the artificially compounded functional bacterial strain solution and the original dominant bacteria strain solution in the biofilm packing tower in proportion to the circulating liquid storage tank of the biofilm packing tower system In the circulating liquid, make it enter the biofilm in the biofilm packed tower to optimize the population structure of desulfurization and denitrification functional bacteria and improve the micro-ecological system, so as to achieve the purpose of improving the simultaneous desulfurization and denitrification efficiency of the biofilm packed tower flue gas.
  • the method of this application has a high removal rate of sulfur dioxide (up to 100%) under the optimal ratio, and the maximum removal rate of nitrogen oxides is only 51%.
  • the removal rate of nitrogen oxides needs to be improved
  • concentration of SO 2 and NOx in the flue gas treated by the method of this application is 2500 ⁇ 3000mg/m 3 and 700 ⁇ 900mg/m 3 respectively .
  • the treatment limit of nitrogen oxides is relatively low, due to the removal rate of this concentration level It is only 51%, and it can be concluded that the method of this application is more difficult to deal with for the removal of high-load nitrogen oxides.
  • Chinese Patent Application No. 201410324904.X discloses a method for adding rare earth intensifiers to improve the denitrification efficiency of a biofilm packed tower for simultaneous flue gas desulfurization and denitrification.
  • a method for adding rare earth intensifiers to improve the denitrification efficiency of a biofilm packed tower for simultaneous flue gas desulfurization and denitrification In the circulating liquid of the circulating liquid storage tank of the packed tower system, add a mixture of low-concentration rare earth elements lanthanum (La) and cerium (Ce) as a bioactive intensifier.
  • La low-concentration rare earth elements lanthanum
  • Ce cerium
  • the SO 2 and NO X concentrations in the flue gas are respectively 500-2000 mg/m 3 and 600-2000 mg/m 3 , and the system's NOx removal rate is 59% to 66%, and the removal effect needs to be improved.
  • the present invention provides a method for simultaneously removing medium and high exhaust gas.
  • a method for loading sulfur dioxide and nitrogen oxides which improves the simultaneous removal efficiency of sulfur dioxide and nitrogen oxides under high load by setting the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas.
  • the present invention provides a method for simultaneously removing high-load sulfur dioxide and nitrogen oxides in exhaust gas.
  • the method passes the exhaust gas into a synchronous desulfurization and denitrification packed tower for exhaust gas removal.
  • the packing of the packed tower is loaded with synchronous removal
  • the microbial flora of sulfur dioxide and nitrogen oxide, the molar concentration ratio of sulfur dioxide and nitrogen oxide in the exhaust gas is (0.76 ⁇ 1.06):1.
  • the microbial flora includes Arthrobacter, Nitrospira, Flavobacterium, Pseudomonas, Rhodococcus, Ralstonia, Hyphomicrobium, Pseudomonas, Rhodococcus, Bacillus, Acinetobacter, Candidatus Acinetobacter, Zoog, a, Dyphosemicrobium , Rhodococcus and Paenibacillus.
  • the microorganism species with nitrification or nitrous acid oxidation function include Arthrobacter, Nitrospira, Flavobacterium, Pseudomonas, Rhodococcus, Ralstonia, and the microorganism species with denitrification function include Pseudomonas, Rhodococcus, Bacillus , Acinetobacter, Candidatus Acinetobacter, Zoogloea, the microbial species with sulfurization function include Burkholderia, Mycobacterium, Pseudomonas, Rhodococcus.
  • the source of the microbial flora for simultaneous removal of sulfur dioxide and nitrogen oxides includes biological sludge.
  • the concentration of sulfur dioxide in the exhaust gas is 2700-3600 mg/m 3 .
  • the concentration of nitrogen oxides in the exhaust gas is 1680-2300 mg/m 3 .
  • the filler loaded in the packed tower includes acid-resistant porous particulate material.
  • the diameter of the filler is 50-200 mm.
  • the method specifically includes the following steps:
  • the operating temperature of the packed tower is controlled to be 25-35°C.
  • the reagents contained in the nutrient solution include FeSO 4 ⁇ 7H 2 O, K 2 HPO 4 ⁇ 3H 2 O, KCl, Ca(NO 3 ) 2 ⁇ 4H 2 O, CH 3 COONa ⁇ 3H 2 O and MgSO 4 .7H 2 O, the pH of the nutrient solution is 2.5.
  • the air flow rate of the packed tower is controlled to be 0.1-0.3m 3/ h, the gas residence time is 100-130 seconds, and the liquid-to-gas ratio in the packed tower is 30-50L/m 3 .
  • the method of the present invention for simultaneous removal of high-load sulfur dioxide and nitrogen oxides in exhaust gas is achieved by setting the molar concentration ratio of SO 2 and NOx in the exhaust gas at the inlet to (0.76 ⁇ 1.06): 1 to the high concentration in the flue gas
  • the method has a treatment concentration of sulfur dioxide in the exhaust gas of 2700 ⁇ 3600mg/m 3 , and a treatment concentration of nitrogen oxides of 1680 ⁇ 2300mg/m 3 , while the existing technology is simultaneously removing sulfur dioxide
  • the system has relatively low treatment concentration of nitrogen oxides, and the removal rate is not high.
  • the method of the present invention simultaneously removes sulfur dioxide and nitrogen oxides with high removal rates. Among them, the removal rate of SO 2 is relatively high. The average removal rate reached 100%, and the average removal rate of NOx reached 78%.
  • the method of the present invention for simultaneous removal of sulfur dioxide and nitrogen oxides in exhaust gas is achieved by setting the molar concentration ratio of SO 2 and NOx in the exhaust gas at the inlet to (0.76 ⁇ 1.06):1, and the biofilm is within this concentration range
  • the microbial system in the packed tower has a synergistic effect during the biochemical reaction of nitrification, denitrification and sulfidation. During the reaction, NOx is converted into nitric acid and SO 2 is converted into sulfuric acid, which greatly improves the removal efficiency of SO 2 and NOx in the exhaust gas. Synchronous desulfurization and denitrification tower systems that exceed this range have a relatively low removal rate of nitrogen oxides, and cannot achieve the improvement of the simultaneous removal efficiency of desulfurization and denitrification.
  • the method of the present invention for simultaneous removal of sulfur dioxide and nitrogen oxides in exhaust gas can still exert a good removal effect when the pH value of the system is less than 1.0 during the reaction process, indicating that the method enables the microorganisms that function in the system
  • the colony can still maintain high activity at extremely low pH values.
  • the method of the present invention only needs to adjust the ratio of SO 2 and NOx at the inlet, which is compared with the method of the prior art It is easier to operate and realize, without adding additional costs, which is conducive to promotion.
  • the method of the present invention for simultaneously removing high-load sulfur dioxide and nitrogen oxides in exhaust gas only needs to inoculate the microbial flora in the biofilm packing tower, and at the same time provide the nutrient solution required by the microbial flora; and the microbial flora can come from
  • the biological sludge in the biochemical treatment system can make the treatment of nitrogen oxides and sulfur dioxide continue and stably proceed without continuous addition of other chemical substances during the operation process, and the nitrogen oxides and sulfur dioxide can be fully converted into nitric acid and sulfuric acid during the treatment process. Or nitrogen can realize the improvement of the simultaneous removal efficiency of nitrogen oxides and sulfur dioxide.
  • the method of the present invention does not need to adjust the pH value during the operation of the system, and can also realize the recycling of acid liquid.
  • Figure 1 is a schematic structural diagram of a biofilm packing tower used in Example 1;
  • Figure 2 shows the change trend of SO 4 2- concentration in the R1 and R2 packed tower system in Example 5;
  • Figure 3 shows the change trend of NO 3 - and NO 2 - concentration in the R1 and R3 packed tower system in Example 5;
  • Figure 4 shows the change trend of pH value in the R1, R2 and R3 packed tower system in Example 5;
  • Figure 5 shows the SO 2 removal level of the R1 packed tower system in Example 5;
  • Figure 6 shows the NOx removal level of the R1 packed tower system in Example 5.
  • Figure 7 shows the SO 2 removal level of the R2 packed tower system in Example 5.
  • Figure 8 shows the NOx removal level of the R3 packed tower system in Example 5.
  • Figure 9 shows the differences in the level of microbial community genus in the R1, R2 and R3 packed tower systems in Example 5.
  • Air inlet 2. Flow meter; 3. Air inlet pipeline; 4. Filling container; 5. Spraying device; 6. Exhaust outlet; 7. Nutrient solution inflow pipeline; 8. Peristaltic pump; 9. , Nutrient solution storage container; 10. Nutrient solution outflow pipeline.
  • the exhaust gas in this embodiment comes from the simulated flue gas generated by the gas generating device.
  • the simulated flue gas is first introduced into the mixing device to mix the simulated flue gas and air.
  • the biofilm packing tower air inlet 1, gas flow meter 2, air inlet pipe 3, packing container 4, and nutrient solution spray device for simultaneous removal of high-load sulfur dioxide and nitrogen oxides of this embodiment 5.
  • the air inlet 1 is used for exhaust gas to enter the packed tower, pass the gas in through the air inlet 1, and enter the packing container 4 of the packed tower through the air inlet pipe 3. This process is set in the inlet pipe 3
  • the gas flow meter 2 on the upper side regulates the gas flow, and the generated gas is discharged through the top of the filling container 4, which is used to load the filler, and the filler is loaded with microorganisms that simultaneously remove sulfur dioxide and nitrogen oxides.
  • the nutrient solution spraying device 5 is provided at the upper end of the filling container 4, and the nutrient solution spraying device 5 is used to evenly spray the nutrient solution; during operation, the nutrient solution is sprayed from the upper end and passes through the biofilm filler of the filling container 4 The nutrient solution flows out from the bottom and enters the nutrient solution storage container 9 through the nutrient solution inflow pipe 7.
  • the nutrient solution inflow pipe 7 is arranged between the nutrient solution storage container 9 and the nutrient solution spray device 5, and
  • the nutrient solution inflow pipeline 7 is provided with a peristaltic pump 8, so the nutrient solution in the nutrient solution storage container 9 can be returned to the nutrient solution spraying device 5 at the top through the peristaltic pump 8, and can be sprayed repeatedly during the operation of the packed tower use.
  • Baffles are respectively provided at the lower end and the middle of the filler container 4 for fixing the microbe-loaded filler.
  • the filler in this embodiment is ceramsite particles with a diameter of 5mm, and the ceramsite particles are inoculated with 10g of sludge taken from the biochemical pond of the sewage treatment system.
  • the biological sludge provides the packed tower for simultaneous removal of sulfur dioxide And nitrogen oxide microorganisms.
  • the method for simultaneously high-load removal of sulfur dioxide and nitrogen oxides from exhaust gas specifically includes the following steps:
  • the nutrient solution is added to the packed tower, and the waste gas to be treated is passed into the packed tower system.
  • the molar concentration ratio of sulfur dioxide and nitrogen oxide in the waste gas in this embodiment is (0.76 ⁇ 1.06):1, and the air inlet is at 1
  • the concentration of sulfur dioxide is 2700 ⁇ 3600mg/m 3
  • the concentration of nitrogen oxides is 1680 ⁇ 2300mg/m 3 .
  • the desulfurization and denitrification treatment is performed in an aerobic environment, the aerobic environment is provided by air, the oxygen concentration in the air is 20%, and the air flow rate is set to be maintained at 0.1m 3 /h, The gas residence time is 100 seconds, and the liquid-gas ratio is 30L/m 3 .
  • the reaction temperature of the packed tower is controlled to be 25°C, and the nutrient solution is sprayed at a rate of 8L/h. After being collected at the bottom, it is returned to the nutrient solution spray device 5 through the peristaltic pump 8. Replenish 20% of the liquid every week, and update the whole every two weeks;
  • the preparation process of the nutrient solution formula is as follows: the solution volume is 1.0L reagent proportioning dose, the chemical reagent is added by weight, and the pH is adjusted to 2.5 with dilute sulfuric acid, and the chemical reagent includes FeSO 4 ⁇ 7H 2 O , K 2 HPO 4 ⁇ 3H 2 O, KCl, Ca(NO 3 ) 2 ⁇ 4H 2 O, CH 3 COONa ⁇ 3H 2 O and MgSO 4 ⁇ 7H 2 O, wherein the FeSO 4 ⁇ 7H 2 O is in the nutrient solution
  • the mass concentration of the K 2 HPO 4 ⁇ 3H 2 O is 0.23 g/L; the mass concentration of the K 2 HPO 4 ⁇ 3H 2 O is 0.655 g/L; the mass concentration of the KCl is 0.1 g/L; the Ca(NO 3 ) 2 ⁇
  • the mass concentration of 4H 2 O is 0.01 g/L, the mass concentration of CH 3 COONa ⁇ 3H 2 O is 0.498
  • the concentration of sulfur dioxide and nitrogen oxides in the exhaust gas at the outlet After running for 2 cycles, detect the concentration of sulfur dioxide and nitrogen oxides in the exhaust gas at the outlet; after testing, the concentration of sulfur dioxide at 6 exhaust ports is less than 100mg/m 3 , with an average value of 2mg/m 3 ; the removal rate is 99%-100%. The average value is 99.9%; the nitrogen oxide concentration is 160-615 mg/m 3 , the average value is 415 mg/m 3 , the removal rate is 66% to 92%, and the average value is 77.5%.
  • This embodiment is basically the same as embodiment 1, except that:
  • the concentration of sulfur dioxide at the air inlet 1 is 2850-3050 mg/m 3
  • the concentration of nitrogen oxides is 2150-2230 mg/m 3
  • the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas is 0.76:1.
  • the filler is ceramsite with a diameter of 200mm.
  • the desulfurization and denitrification treatment in step 2) is carried out in an aerobic environment.
  • the aerobic environment is provided by air.
  • the oxygen concentration in the air is 20%.
  • the flow rate is maintained at 0.2m 3 /h, the gas residence time is 110 seconds, and the liquid-gas ratio is 40L/m 3 .
  • the temperature of the packed tower during operation is 35°C.
  • This embodiment is basically the same as embodiment 1, except that:
  • the concentration of sulfur dioxide at the intake port 1 is 2930-3000 mg/m 3
  • the concentration of nitrogen oxides is 1680-2000 mg/m 3
  • the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas is 1.06:1.
  • the filler is a porous acid-resistant plastic material with a diameter of 100 mm.
  • the desulfurization and denitrification treatment in step 2) is performed in an aerobic environment, the aerobic environment is provided by air, and the oxygen concentration in the air is 20 %, set the air flow rate to be kept at 0.2m 3 /h, the gas residence time to be 110 seconds, and the liquid to gas ratio to be 40L/m 3 .
  • the temperature of the packed tower during operation is 30°C.
  • This embodiment is basically the same as embodiment 1, except that:
  • the sulfur dioxide concentration at the inlet was 1 2700 ⁇ 3600mg / m 3
  • the concentration of nitrogen oxides is 1800 ⁇ 2300mg / m 3
  • the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas was 0.9: 1.
  • This embodiment is basically the same as embodiment 1, except that:
  • the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas is (0.66 ⁇ 0.76):1
  • the sulfur dioxide concentration at the air inlet 1 is 2500-3450 mg/m 3
  • the nitrogen oxide concentration is 2250 ⁇ 2650mg/m 3 .
  • the concentration of sulfur dioxide and nitrogen oxide in the exhaust gas at the outlet is 0-20mg/m 3 , with an average value of 1.3mg/m 3 ; the removal rate is 99%-100 %, average 99.9%; nitrogen oxide concentration of 600 ⁇ 910mg / m 3, the average value of 791mg / m 3, the removal rate of 62% to 74%, the average 68.1%.
  • This embodiment is basically the same as embodiment 1, except that:
  • the molar concentration ratio of sulfur dioxide and nitrogen oxides in the exhaust gas is (1.06-1.56):1
  • the sulfur dioxide concentration at the air inlet 1 is 2450-3450 mg/m 3
  • the nitrogen oxide concentration is 1000- 1750mg/m 3 .
  • the concentration of sulfur dioxide and nitrogen oxide in the exhaust gas at the outlet is 0 ⁇ 223mg/m 3 , with an average value of 103mg/m 3 ; removal rate is 93% ⁇ 100% , The average value is 97.0%; the nitrogen oxide concentration is 200-787mg/m 3 , the average value is 448mg/m 3 , the removal rate is 36%-82%, and the average value is 65.2%.
  • Table 1 shows the statistics of the simultaneous removal of sulfur dioxide and nitrogen oxides in the examples and comparative examples.
  • the present invention verifies the mechanism of removing sulfur dioxide and nitrogen oxides from flue gas at the same time.
  • a series of reactors are set up, and the devices set up are the biofilm packing towers R1, R2, R3 running in parallel, where R1 is Simultaneous removal of biofilm packing tower, R2 is a separate denitrification biological packing tower, R3 is a separate desulfurization biological tower,
  • the simulated flue gas containing nitrogen oxides and sulfur dioxide is fed into the above biological towers to perform desulfurization and denitrification treatment in an aerobic environment;
  • the microbial flora has nitrification, denitrification, sulfurization and desulfurization functions, in which nitrification and denitrification reactions
  • the sulfurization reaction is the main action mechanism to remove sulfur dioxide.
  • the present invention studies the reaction mechanism of the oxidation of nitrogen oxides and sulfur dioxide to produce nitric acid and sulfuric acid under the mediation of microorganisms, and the main microbial community types that mediate the reaction.
  • the average outlet gas concentration of SO 2 is maintained at less than 100 mg/m 3 , and the NOx is 160-620 mg/m 3 , including 108-463 mg/m 3 NO and 22-187 mg/m 3 NO 2 .
  • the SO 2 concentration is far lower than the SO 2 emission concentration limit (400 mg/m 3 ) of the Chinese Boiler Air Pollutant Emission Standard (GB 13271-2014), which meets the emission requirements.
  • a part (approximately 15%) of SO 4 2- and NO 3 - may be retained in the filler voids in the form of adsorption, which also leads to the occurrence of a plateau, and when the nutrient solution is supplemented by about 20%, SO 4 2- and NO 3 - Rapid recovery of concentration.
  • the NO 3 - concentration is significantly higher (p ⁇ 0.05) than the molar concentration (77.8%) of the solution in the simultaneous removal of low-load sulfur dioxide and nitrogen oxides, and in the microbial system, the denitrification microorganisms Pseudomonas and Rhodococcus
  • the relative abundance decreased significantly (Pseudomonas decreased from 52.7% to 1.0%, Rhodococcus decreased from 19.2% to 0.6%), while the relative abundance of nitrifying microorganisms such as Arthrobacter, Nitrospira, Flavobacterium, and Hyphomicrobium increased to 1% of the total abundance of all microorganisms. % ⁇ 2%, indicating that the nitrogen oxide removal reaction system reduces nitrogen removal and increases nitrogen oxide oxidation.
  • the SO 4 2- is significantly lower (p ⁇ 0.05) than the molar concentration of the solution in the simultaneous removal of low load (84.8%). And the appearance of desulfurization microorganism Paenibacillus, indicating that a part of the SO 4 2- that enters the solution is used by microorganisms, reduced to elemental sulfur and stored in the cells, which is also consistent with the sulfur color characteristics of the microbial community on the surface of the filler. Therefore, in the reaction system of the present invention, there is a sulfate radical reduction desulfurization reaction:
  • Figure 2 is the comparison of the change trend of SO 4 2- concentration in the circulating nutrient solution of the R1 and R2 packed tower systems in this embodiment
  • Figure 3 is the NO 3 - and NO 2 in the circulating nutrient solution of the R1 and R3 packed tower systems in this embodiment - change of the concentration of contrast
  • the SO 2 discharge concentration of the single desulfurization biological packing tower R2 is 0 ⁇ 1151mg/m 3 ; and the NOx discharge concentration of the single denitrification biological packing tower R3 is 536 ⁇ 810 mg/m 3 , Including 275 ⁇ 643mg/m 3 NO and 135 ⁇ 422mg/m 3 NO 2 .
  • Figure 5 shows the SO 2 removal level of the R1 packed tower system in Example 5;
  • Figure 6 shows the NOx removal level of the R1 packed tower system in Example 5;
  • Figure 7 shows the SO 2 removal level of the R2 packed tower system in Example 5
  • Figure 8 shows the NOx removal level of the R3 packed tower system in Example 5.
  • the microorganisms include nitrifying microorganisms, denitrifying microorganisms and sulfur microorganisms. Specific microbial species with nitrification or nitrous acid oxidation function, microbial species with denitrification function, and microbial species with sulfurization and desulfurization functions.
  • Figure 9 shows the level of microbial community in the R1, R2 and R3 packed tower system difference.
  • the microorganism species with nitrification or nitrous acid oxidation function include Arthrobacter, Nitrospira, Flavobacterium, Pseudomonas, Rhodococcus, Ralstonia and Hyphomicrobium, and the microorganism species with denitrification function include Pseudomonas, Rhodococcus, Bacillus , Acinetobacter, Candidatus Acinetobacter, Zoogloea and Hyphomicrobium, the microbial species with sulfurization function include Dietzia, Burkholderia, Mycobacterium, Pseudomonas, Rhodococcus, and the microbial species with desulfurization function include Paenibacillus.
  • Table 2 shows the comparison of the removal effects of different biological packing towers.

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Abstract

一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法，属于生物法工业废气净化技术领域。该方法将废气通入同步脱硫脱氮填料塔进行废气脱除，填料塔的填料上负载有同步脱除二氧化硫和氮氧化物的微生物菌群，废气中二氧化硫和氮氧化物的摩尔浓度比为(0.76～1.06)：1。

Description

一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法 技术领域
本发明涉及生物法工业废气净化技术领域，具体涉及一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法。
背景技术
硫氧化物SO X和氮氧化物NO X是主要的空气污染物，是由化石燃料燃烧过程中排放出来的。氮氧化物NO X含有多种化合物，其中NO和NO 2为主要污染物，而且由于它们在光化学烟雾，酸雨和臭氧层破坏剂中的作用而引发严重的环境问题。二氧化硫SO 2是硫氧化物SO X中最主要部分，占96％以上，因而一般可以SO 2代表硫氧化物。SO 2直接导致酸雨形成和臭氧层的缺失。由于SO X和NO X排放和环境污染日益受到关注，烟气的清洁过程引起了人们的广泛关注。中国生态与环境部报告显示发电厂和工业锅炉的二氧化硫和氮氧化物总产量分别为0.16亿和0.12亿吨，占总排放量的约90％和70％，是最主要的二氧化硫和氮氧化物来源。
传统烟气净化过程中的主要障碍是以有效和环保的方式处理含有污染物的溶剂和固体吸附剂。但是，简单地将二氧化硫和氮氧化物视为污染物不利于硫和氮元素的资源再利用和实现循环经济。事实上，含有SO X，NO X，CO 2等成分的烟气可以提供液体或气溶胶中的养分，作为微生物生长的基质。生物过滤器因其经济实惠、可以在环境温度下保持高效的工作效率、无需维护、长寿命、低运行成本和环境友好性等优势，成为烟气处理中最常用的技术之一。但是，当前制约微生物过滤器推广使用的一大瓶颈在于，生物过滤器较物理化学方法处理量普遍偏低，处理负荷亟待提高，否则难以适应日益提高的社会化大生产需要。究其原因，乃是与物理化学方法相比，生物法处理技术的原理和分子机制研究不透彻，限制了生物法处理烟气效率的进一步提升和改良。
经检索，利用微生物同步脱除二氧化硫和氮氧化物的方法已经得到公开，如中国专利申请号201110124316.8，公开日期为2013年8月14日的申请案公开了一种通过人工复配功能菌以提高生物膜填料塔烟气同时脱硫脱氮效率的技术方法。其应用单个生物膜填料塔烟气同时脱硫脱氮系统，通过将人工复配功能菌菌株液与生物膜填料塔中原有优势菌的菌株液按比例添加到生物膜填料塔系统循环液储槽的循环液体中，使之进入生物膜填料塔中的生物膜去优化脱硫脱氮功能菌的种群结构及改善微生态系统，从而达到提高生物膜填料塔烟气同时脱硫脱氮效率的目的。该申请案的方法在最佳配比条件下对二氧化硫脱除率较高(最高可达100％)，对氮氧化物的去除率最高仅达到51％，对氮氧化物的去除率还有待改善，该申请案 的方法所处理的烟气SO 2和NOx浓度分别为2500～3000mg/m 3和700～900mg/m 3，其中对氮氧化物的处理限度较低，由于该浓度水平的去除率仅为51％，可以得出该申请案的方法在针对高负荷的氮氧化物的去除时，处理难度较大。
由于生物膜方法进行脱除烟气中二氧化硫(SO 2)和氮氧化物(NOx)时包括硝化、反硝化和硫化等一系列的反应过程，填料塔中负载的微生物多样性较高，每种微生物适合pH范围差异较大，主要脱除SO 2的微生物可以具有一定的耐酸性，而脱除氮氧化物(NOx)的微生物在极低的酸性条件下适应性较差，为了解决上述问题，现有技术中也公开了相关的解决方法。如中国专利申请号200910218315.2，公开日期为2015年8月19日的申请案公开了一种双塔串联式催化-生物膜填料塔系统同时脱除烟气中二氧化硫和氮氧化物的方法，其采用前面一个使用催化氧化剂循环喷淋液的生物膜填料塔系统和后面一个使用pH缓冲剂循环喷淋液的生物膜填料塔系统的双塔串联式烟气净化处理组合装置，前面的生物膜填料塔系统在pH酸性条件下操作，主要脱除SO 2附带脱除小部分NOx，其副产物以硫酸为主并附带少量硝酸；后面的生物膜填料塔系统在pH中性条件下操作，脱除剩余的NOx，其副产物则主要是硝酸；进行同时脱除烟气中二氧化硫(SO 2)和氮氧化物(NOx)的净化处理并副产可利用硫酸硝酸产品。该申请案采用双塔串联的方式进行SO 2和NOx脱除，对SO 2和NOx的净化效率均比采用原有单一生物膜填料塔系统净化技术时有明显提高，但采用双塔串联在一定程度上增加了操作成本。
中国专利申请号201410324904.X，公开日期为2016年6月15日的申请案公开了一种外加稀土强化剂提高烟气同时脱硫脱氮用生物膜填料塔脱氮效率的方法，其在生物膜填料塔系统循环液储槽的循环液中，加入低浓度稀土元素镧(La)和铈(Ce)的混合物作为生物活性强化剂，搅拌均匀后通过循环泵使其随循环液体喷淋到塔内的生物膜上，用以刺激及改善以自养菌为主的微生物菌群中的脱氮菌群对低pH强酸性生长环境条件的适应性，从而促进脱氮菌群的快速生长繁殖，以获得提高烟气同时脱硫脱氮用生物膜填料塔脱氮效率的效果。该申请案的方法在烟气中SO 2和NO X浓度分别为500～2000mg/m 3和600～2000mg/m 3，系统NOx的去除率为59％～66％，去除效果还有待改善。
同时对同步脱除烟气中二氧化硫和氮氧化物的化学反应机理和微生物群落结构和对应的分子机制的研究仍不透彻，对进一步改良改进该方法，最大化生物处理的益处带来了很大困难，造成了方法进一步推广、产业化、实用化的瓶颈。
发明内容
1.要解决的问题
针对现有技术中同时脱除二氧化硫和氮氧化物的生物膜填料塔同步针对氮氧化物的去除 存在处理浓度相对较低且去除率不高的缺陷，本发明提供了一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法，该方法通过设定废气中的二氧化硫和氮氧化物的摩尔浓度比来提高高负荷下的二氧化硫和氮氧化物的同步去除效率。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
本发明提供了一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法，所述方法将废气通入同步脱硫脱氮填料塔进行废气脱除，所述填料塔的填料上负载有同步脱除二氧化硫和氮氧化物的微生物菌群，所述废气中二氧化硫和氮氧化物的摩尔浓度比为(0.76～1.06)：1。
作为本发明更进一步的改进，所述微生物菌群包括Arthrobacter、Nitrospira、Flavobacterium、Pseudomonas、Rhodococcus、Ralstonia、Hyphomicrobium、Pseudomonas、Rhodococcus、Bacillus、Acinetobacter、Candidatus Acinetobacter、Zoogloea、Hyphomicrobium、Dietzia、Burkholderia、Mycobacterium、Pseudomonas、Rhodococcus和Paenibacillus。
作为本发明更进一步的改进，所述具有硝化或亚硝酸氧化功能的微生物种属包括Arthrobacter、Nitrospira、Flavobacterium、Pseudomonas、Rhodococcus、Ralstonia，所述具有脱氮功能的微生物种属包括Pseudomonas、Rhodococcus、Bacillus、Acinetobacter、Candidatus Acinetobacter、Zoogloea，所述具有硫化功能的微生物种属包括Burkholderia、Mycobacterium、Pseudomonas、Rhodococcus。
作为本发明更进一步的改进，所述同步脱除二氧化硫和氮氧化物的微生物菌群来源包括生物污泥。
作为本发明更进一步的改进，所述废气中二氧化硫的浓度为2700～3600mg/m 3，
作为本发明更进一步的改进，所述废气中氮氧化物的浓度为1680～2300mg/m 3。
作为本发明更进一步的改进，所述填料塔中负载的填料包括耐酸多孔颗粒材料。
作为本发明更进一步的改进，所述填料的直径为50～200mm。
作为本发明更进一步的改进，所述方法具体包括以下步骤：
a)将营养液加入至所述填料塔中；
b)将待处理废气与空气混合后通入所述填料塔中进行处理，控制所述填料塔的运行温度；
c)从所述填料塔上部喷洒营养液，所述营养液从底部流出后再通过蠕动泵重新回流至所述填料塔上部循环喷洒；
d)所述填料塔系统产生的气体通过设置在填料塔顶部的出气口排出。
作为本发明更进一步的改进，所述步骤b)中控制所述填料塔运行温度为25～35℃。
作为本发明更进一步的改进，所述营养液中含有的试剂包括FeSO 4·7H 2O、K 2HPO 4·3H 2O、 KCl、Ca(NO 3) 2·4H 2O、CH 3COONa·3H 2O和MgSO 4·7H 2O，所述营养液的pH值为2.5。
作为本发明更进一步的改进，所述填料塔运行时控制空气流量为0.1～0.3m 3/h，气体停留时间为100～130秒，所述填料塔内的液气比为30～50L/m 3。
3.有益效果
相比于现有技术，本发明的有益效果为：
(1)本发明的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，通过设定入口处废气中SO 2和NOx的摩尔浓度比为(0.76～1.06)：1对烟气中的高浓度的氮氧化物和二氧化硫进行处理，该方法对废气中二氧化硫的处理浓度达到2700～3600mg/m 3，对氮氧化物的处理浓度达到1680～2300mg/m 3，而现有技术中在同步去除二氧化硫和氮氧化物时，存在系统对氮氧化物的处理浓度相对较低，且去除率不高的缺陷，本发明的方法同步去除二氧化硫和氮氧化物的去除率均较高，其中对SO 2的去除率平均值达到100％，对NOx的去除率平均值达到78％。
(2)本发明的同时脱除废气中二氧化硫和氮氧化物的方法，通过设定入口处废气中SO 2和NOx的摩尔浓度比为(0.76～1.06)：1，在该浓度范围内生物膜填料塔中微生物系统进行硝化、反硝化和硫化的生化反应时出现协同作用，在反应过程中将NOx转化为硝酸并将SO 2转化为硫酸，大大提高废气中SO 2和NOx脱除效率，而超过该范围的同步脱硫脱氮塔系统则对氮氧化物的去除率相对较低，无法实现脱硫脱氮同步去除效率的提升。
(3)本发明的同时脱除废气中二氧化硫和氮氧化物的方法，在反应过程中系统的pH值<1.0时仍能发挥较好的去除效果，说明该方法使系统中发挥作用的微生物菌群在极低pH值依然能保持较高的活性，而现有技术中则需要加入生物活性强化剂以刺激及改善以菌群对低pH强酸性生长环境条件的适应性，从而刺激增殖，进而产生较好的废气去除效果，或者设置两种不同pH值的生物填料塔以提高废气去除效果；本发明的方法则只需要调整入口处SO 2和NOx的比例，与现有技术的方法相比更容易操作和实现，不需要增加额外成本，利于推广。
(4)本发明的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，只需在生物膜填料塔中接种微生物菌群，同时提供微生物菌群所需的营养液；而微生物菌群可来自于生化处理系统的生物污泥，在运行过程中无需持续添加其他化学物质即可使得氮氧化物和二氧化硫的处理持续稳定进行，处理过程中能够将氮氧化物和二氧化硫充分转换为硝酸、硫酸，或氮气，实现氮氧化物和二氧化硫的同步去除效率的提高，另一方面，本发明的方法在系统运行过程中无需调整pH值，还可以实现酸液的回收利用。
附图说明
图1为实施例1采用的生物膜填料塔的结构示意图；
图2为实施例5中R1和R2填料塔系统中SO 4 2-浓度的变化趋势；
图3为实施例5中R1和R3填料塔系统中NO 3 -和NO 2 -浓度的变化趋势；
图4为实施例5中R1、R2和R3填料塔系统中pH值的变化趋势；
图5为实施例5中R1填料塔系统对SO 2脱除水平；
图6为实施例5中R1填料塔系统对NOx的脱除水平；
图7为实施例5中R2填料塔系统对SO 2的脱除水平；
图8为实施例5中R3填料塔系统对NOx的脱除水平；
图9为实施例5中R1、R2和R3填料塔系统中微生物群落属水平差异。
图中，1、进气口；2、流量计；3、进气管路；4、填料容器；5、喷洒装置；6、排气口；7、营养液流入管路；8、蠕动泵；9、营养液储存容器；10、营养液流出管路。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
本实施例的废气来自气体发生装置产生的模拟烟气，在进入同步脱硫脱氮填料塔处理前首先将模拟烟气通入混合装置，对模拟烟气和空气进行混合。
如图1所示，本实施例的同步脱除高负荷的二氧化硫和氮氧化物的生物膜填料塔进气口1、气体流量计2、进气管路3、填料容器4、营养液喷淋装置5、排气口6、营养液流入管路7、蠕动泵8、营养液储存容器9和营养液流出管路10。
所述进气口1用于废气气体进入所述填料塔，将气体通过进气口1通入，通过进气管路3进入所述填料塔的填料容器4，该过程通过设置在进气管路3上的气体流量计2调控气体流量，产生的气体通过设置在所述填料容器4顶端排出，所述填料容器4用于装载填料，所述填料上负载同步脱除二氧化硫和氮氧化物的微生物，所述填料容器4上端设置营养液喷淋装置5，所述营养液喷淋装置5用于将营养液的均匀喷洒；在运行过程中，营养液从上端喷洒，经过填料容器4的生物膜填料区并从底部流出，流出的营养液由营养液流入管路7进入营养液储存容器9，所述营养液储存容器9与营养液喷淋装置5之间设置营养液流入管路7，并在所述营养液流入管路7上设置蠕动泵8，因此营养液储存容器9中的营养液可以通过蠕动泵8回流至顶部的营养液喷淋装置5，在所述填料塔运行中可以重复喷洒利用。在所述填料容器4的下端和中部分别设置有挡板，用于固定负载微生物的填料。
本实施例中的填料为直径为5mm的陶粒颗粒，所述陶粒颗粒上接种有取自来自污水处理系统生化池中污泥10g，所述的生物污泥为填料塔提供同步脱除二氧化硫和氮氧化物的微生物。
本实施例中进行废气中同时高负荷脱除二氧化硫和氮氧化物的方法具体包括以下步骤：
1)将营养液加入填料塔中，将待处理废气通入填料塔系统，本实施例废气中二氧化硫和氮氧化物的摩尔浓度比为(0.76～1.06)：1，所述进气口1处的二氧化硫浓度为2700～3600mg/m 3，氮氧化物的浓度为1680～2300mg/m 3。
2)在实施例中所述脱硫脱氮处理在好氧环境下进行，所述好氧环境由空气提供，所述空气中的氧气浓度为20％，设置空气流量保持在0.1m 3/h，气体停留时间为100秒，液气比为30L/m 3。
3)所述填料塔运行过程中控制填料塔反应温度为25℃，所述营养液以8L/h的速率喷洒，在底部汇集后通过蠕动泵8回流至营养液喷淋装置5循环喷洒，营养液每周补充20％，每两周更新全部；
所述营养液配方的配制过程为：以溶液体积为1.0L的试剂配比剂量，按重量加入化学试剂，并以稀硫酸调节pH为2.5制成，所述化学试剂包括FeSO 4·7H 2O、K 2HPO 4·3H 2O、KCl、Ca(NO 3) 2·4H 2O、CH 3COONa·3H 2O和MgSO 4·7H 2O，其中所述FeSO 4·7H 2O在营养液中的质量浓度为0.23g/L；所述K 2HPO 4·3H 2O的质量浓度为0.655g/L；所述KCl的质量浓度为0.1g/L；所述Ca(NO 3) 2·4H 2O的质量浓度为0.01g/L、所述CH 3COONa·3H 2O的质量浓度为0.498g/L；所述MgSO 4·7H 2O的质量浓度为0.5g/L。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度小于100mg/m 3，，平均值为2mg/m 3；去除率为99％～100％，平均值为99.9％；氮氧化物浓度为160～615mg/m 3，平均值为415mg/m 3，去除率为66％～92％，平均值为77.5％。
实施例2
本实施例基本与实施例1相同，不同之处在于：
本实施例所述进气口1处的二氧化硫浓度为2850～3050mg/m 3，氮氧化物的浓度为2150～2230mg/m 3，废气中二氧化硫和氮氧化物的摩尔浓度比为0.76：1。
所述填料为直径为200mm的陶粒，步骤2)中所述脱硫脱氮处理在好氧环境下进行，所述好氧环境由空气提供，所述空气中的氧气浓度为20％，设置空气流量保持在0.2m 3/h，气体停留时间为110秒，液气比为40L/m 3。
所述填料塔运行时温度为35℃。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度为0～30mg/m 3，去除率为99％～100％，平均值为99.9％；氮氧化物浓度为160～390mg/m 3，去除率为80％～92％，平均值为85.4％。
实施例3
本实施例基本与实施例1相同，不同之处在于：
本实施例所述进气口1处的二氧化硫浓度为2930～3000mg/m 3，氮氧化物的浓度为1680～2000mg/m 3，废气中二氧化硫和氮氧化物的摩尔浓度比为1.06：1。
所述填料为直径为100mm的多孔耐酸塑料材质，所述步骤2)中所述脱硫脱氮处理在好氧环境下进行，所述好氧环境由空气提供，所述空气中的氧气浓度为20％，设置空气流量保持在0.2m 3/h，气体停留时间为110秒，液气比为40L/m 3。
所述填料塔运行时温度为30℃。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度为0～80mg/m 3，去除率为98％～100％，平均值为99.5％；氮氧化物浓度为260～300mg/m 3，去除率为78％～85％，平均值为81.0％。
实施例4
本实施例基本与实施例1相同，不同之处在于：
本实施例所述进气口1处的二氧化硫浓度为2700～3600mg/m 3，氮氧化物的浓度为1800～2300mg/m 3，废气中二氧化硫和氮氧化物的摩尔浓度比为0.9：1。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度为0～30mg/m 3，去除率为99％～100％，平均值为99.9％；氮氧化物浓度为190～600mg/m 3，去除率为66％～89％，平均75.4％。
对比例1
本实施例基本与实施例1相同，不同之处在于：
本实施例中废气中二氧化硫和氮氧化物的摩尔浓度比为(0.66～0.76)：1，所述进气口1处的二氧化硫浓度为2500～3450mg/m 3，氮氧化物的浓度为2250～2650mg/m 3。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度为0～20mg/m 3，平均值为1.3mg/m 3；去除率为99％～100％，平均值为99.9％；氮氧化物浓度为600～910mg/m 3，平均值为791mg/m 3，去除率为62％～74％，平均值为68.1％。
对比例2
本实施例基本与实施例1相同，不同之处在于：
本实施例中废气中二氧化硫和氮氧化物的摩尔浓度比为(1.06～1.56)：1，所述进气口1处的二氧化硫浓度为2450～3450mg/m 3，氮氧化物的浓度为1000～1750mg/m 3。
运行2个周期后检测出口废气中二氧化硫和氮氧化物浓度；经检测，排气口6处二氧化硫浓度为0～223mg/m 3，平均值为103mg/m 3；去除率为93％～100％，平均值为97.0％；氮氧化物浓度为200～787mg/m 3，平均值为448mg/m 3，去除率为36％～82％，平均值为65.2％。
表1为实施例及对比例中同步脱除二氧化硫和氮氧化物的结果统计。
表1实施例1及对比例中同步脱除二氧化硫和氮氧化物的结果统计
Figure PCTCN2020073446-appb-000001
根据表1可知，本发明的方法将SO 2和NOx摩尔浓度比设定为(0.76～1.06)：1时，系统对SO 2去除率平均值可达到100％，对NOx去除率平均值可达到76％，显著的提高了同步脱除效率，而大于或小于该比例范围时，系统对NOx的去除率下降。
实施例5
本发明对同时烟气中脱除二氧化硫和氮氧化物的机理进行了验证，该实施例设置一系列反应器，设置的装置为平行运行的其中生物膜填料塔R1、R2、R3，其中R1为同步脱除生物膜填料塔，R2为单独脱氮生物填料塔，R3为单独脱硫生物塔，
分别对上述生物塔通入含氮氧化物和二氧化硫的模拟烟气在好氧环境下进行脱硫脱氮处理；所述微生物菌群具有硝化、反硝化、硫化和脱硫功能，其中硝化和反硝化反应为脱除氮氧化物的主要作用机制，硫化反应为脱除二氧化硫的主要作用机制。
本发明在好氧的条件下，研究有无微生物介导下，氮氧化物和二氧化硫发生氧化，产生硝酸和硫酸的反应机理，以及介导反应的主要微生物群落类型。
通过监测反应器进出气中二氧化硫、二氧化氮、一氧化氮的浓度，以及反应器循环营养液中硝酸根、硫酸根浓度及溶液pH值，对微生物介导下，氮氧化物和二氧化硫发生氧化，产生硝酸和硫酸的反应机理进行研究。之后，再应用高通量测序技术，对同步和分别脱除模拟烟气中氮氧化物和二氧化硫的微生物分子机制进行研究。
1)生物填料塔R1的研究
本发明在生物填料塔R1中，SO 2的平均出口气体浓度保持在小于100mg/m 3，NOx为160～620mg/m 3，包括108～463mg/m 3 NO和22～187mg/m 3 NO 2。其中SO 2浓度远低于中国锅炉大气污染物排放标准(GB 13271-2014)的SO 2排放浓度限值(400mg/m 3)，符合排放要求。
在反应器稳定运行第3周期后，R1中SO 2和NOx的去除呈显著相关(p<0.05)，其中在第3-7周期中，显著相关(r 2＝0.33，p<0.05)，其协同消除的摩尔量比例为1.16：1(式1)。R1反应器循环营养液中的SO 4 2-和NO 3 -浓度显示出与不同的增加趋势。
a)在初始阶段(第8周期第2-4天)，R1中的SO 4 2-和NO 3 -实现了线性增长；
b)在第4天至第7天，进入一个平台期，SO 4 2-和NO 3 -的生长减缓甚至停止；
c)在第7天营养液补充约20％后，SO 4 2-和NO 3 -浓度S型升高，在完全更换营养液前(第3周期第12-14天)显示加速增长，分别达到23.07g/L和15.93g/L。营养液中SO 4 2-和NO 3 -的浓度为极显著相关(r 2＝0.87，p<0.001)，显示出协同效应，其在溶液中的摩尔浓度比为1.30：1，分别占气体中消除的N元素和S元素摩尔总量的81.0％和81.7％。
一部分(约15％)的SO 4 2-和NO 3 -可能以吸附的形式存留于填料空隙中，这也导致了平台期的出现，和营养液补充约20％时，SO 4 2-和NO 3 -浓度迅速的恢复。但是NO 3 -浓度显著高于(p<0.05)我们之前在低负荷二氧化硫和氮氧化物同步脱除中的溶液中摩尔浓度占比(77.8％)，以及微生物体系中，脱氮微生物Pseudomonas、Rhodococcus相对丰度大幅下降(Pseudomonas从52.7％下降至1.0％，Rhodococcus从19.2％下降至0.6％)，而硝化微生物Arthrobacter、Nitrospira、Flavobacterium、Hyphomicrobium等相对丰度均上升至占所有微生物总丰度的1％～2％，表明氮氧化物脱除的反应体系减少了氮的脱除，而增加了氮氧化物的氧化。
本发明所述反应体系中，由于有脱氮微生物的存在，存在反硝化的氮脱除反应：
Figure PCTCN2020073446-appb-000002
而SO 4 2-显著低于(p<0.05)低负荷同步脱除中的溶液中摩尔浓度占比(84.8％)。和脱硫微生物Paenibacillus的出现，表明一部分进入溶液的SO 4 2-被微生物利用，还原为硫单质存储于细胞内，这也与填料表面微生物群落显示出的硫磺色特征相吻合。因此本发明所述反应体系中，存在硫酸根还原脱硫反应：
Figure PCTCN2020073446-appb-000003
因此，本发明所述微生物催化体系下，氮氧化物和二氧化硫同步脱除反应依照反应式3进行：
Figure PCTCN2020073446-appb-000004
图2为本实施例中R1和R2填料塔系统循环营养液中SO 4 2-浓度的变化趋势对比；图3 为本实施例中R1和R3填料塔系统循环营养液中NO 3 -和NO 2 -浓度的变化趋势对比；图4为本实施例中R1、R2和R3填料塔系统中pH值的变化趋势对比。
2)单独脱硫生物填料塔R2和单独脱氮生物填料塔R3的研究
本发明在其他两个生物反应器中，单独脱硫生物填料塔R2的SO 2排出浓度为0～1151mg/m 3；而单独脱氮生物填料塔R3的NOx排出浓度为536～810mg/m 3，包括275～643mg/m 3NO和135～422mg/m 3 NO 2。
R1与R2和R3之间的进气浓度没有显著差异，R1的性能，即SO 2和NOx的去除率(99.9％和77.5％)显著(p<0.05)优于R2(81.9％，SO 2)或R3(67.7％，NOx)，
图5为实施例5中R1填料塔系统对SO 2脱除水平；图6为实施例5中R1填料塔系统对NOx的脱除水平；图7为实施例5中R2填料塔系统对SO 2的脱除水平；图8为实施例5中R3填料塔系统对NOx的脱除水平。
在本发明中，所述微生物包括硝化微生物、反硝化微生物和硫化微生物。具体的具有硝化或亚硝酸氧化功能的微生物种属、具有脱氮功能的微生物种属、具有硫化功能和脱硫功能的微生物种属，图9为R1、R2和R3填料塔系统中微生物群落属水平差异。
根据图9可知，所述的具有硝化或亚硝酸氧化功能的微生物种属包括Arthrobacter、Nitrospira、Flavobacterium、Pseudomonas、Rhodococcus、Ralstonia和Hyphomicrobium，所述具有脱氮功能的微生物种属包括Pseudomonas、Rhodococcus、Bacillus、Acinetobacter、Candidatus Acinetobacter、Zoogloea和Hyphomicrobium，所述具有硫化功能的微生物种属包括Dietzia、Burkholderia、Mycobacterium、Pseudomonas、Rhodococcus，所述具有脱硫功能的微生物种属包括Paenibacillus。
表2为不同的生物填料塔去除效果对比。
表2不同的生物填料塔去除效果对比
Figure PCTCN2020073446-appb-000005
以上示意性的对本发明及其实施方式进行了描述，该描述没有限制性。所以，如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的结构方式及实施例，均应属于本发明的保护范围。

Claims (10)

  1. 一种同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述方法将废气通入同步脱硫脱氮填料塔进行废气脱除，所述填料塔的填料上负载有同步脱除二氧化硫和氮氧化物的微生物菌群，所述废气中二氧化硫和氮氧化物的摩尔浓度比为(0.76～1.06)：1。
  2. 根据权利要求1所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述微生物菌群包括Arthrobacter、Nitrospira、Flavobacterium、Pseudomonas、Rhodococcus、Ralstonia、Hyphomicrobium、Pseudomonas、Rhodococcus、Bacillus、Acinetobacter、CandidatusAcinetobacter、Zoogloea、Hyphomicrobium、Dietzia、Burkholderia、Mycobacterium、Pseudomonas、Rhodococcus和Paenibacillus。
  3. 根据权利要求1或2所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述同步脱除二氧化硫和氮氧化物的微生物菌群来源包括生物污泥。
  4. 根据权利要求3所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述废气中二氧化硫的浓度为2700～3600mg/m 3，
  5. 根据权利要求4所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述废气中氮氧化物的浓度为1680～2300mg/m 3。
  6. 根据权利要求3所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述填料塔中负载的填料包括耐酸多孔颗粒材料。
  7. 根据权利要求6所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述填料的直径为50～200mm。
  8. 根据权利要求1或2所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述方法具体包括以下步骤：
    a)将营养液加入至所述填料塔中；
    b)将待处理废气与空气混合后通入所述填料塔中进行处理，控制所述填料塔的运行温度；
    c)从所述填料塔上部喷洒营养液，所述营养液从底部流出后再通过蠕动泵重新回流至所述填料塔上部循环喷洒；
    d)所述填料塔系统产生的气体通过设置在填料塔顶部的出气口排出。
  9. 根据权利要求8所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述步骤b)中控制所述填料塔运行温度为25～35℃。
  10. 根据权利要求9所述的同时脱除废气中高负荷二氧化硫和氮氧化物的方法，其特征在于：所述营养液中含有的试剂包括FeSO 4·7H 2O、K 2HPO 4·3H 2O、KCl、Ca(NO 3) 2·4H 2O、CH 3COONa·3H 2O和MgSO 4·7H 2O，所述营养液的pH值为2.5。
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