CN114653190A - Flue gas desulfurization/denitration/cadmium removal membrane bioreactor treatment method - Google Patents
Flue gas desulfurization/denitration/cadmium removal membrane bioreactor treatment method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
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- 239000003546 flue gas Substances 0.000 title claims abstract description 58
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- 230000023556 desulfurization Effects 0.000 title claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 238000003916 acid precipitation Methods 0.000 description 2
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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
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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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention discloses a flue gas desulfurization/denitration/cadmium removal membrane bioreactor treatment method, which comprises the steps of introducing flue gas containing sulfur/nitrate/cadmium into a membrane bioreactor, and performing denitrification, desulfurization, bioadsorption and biostability on a biological membrane after mass transfer of the flue gas through a gas membrane in the membrane bioreactor to realize denitrification and desulfurization and simultaneously convert cadmium in the flue gas; wherein a biological membrane is formed in the membrane bioreactor in a growing way, and the biological membrane consists of one or more of Citrobacter, Desulfurovibrio and Pseudomonas. Compared with physical treatment, the method has the advantages of low cost, capability of converting the cadmium in the flue gas into a more stable form, reduction of the mobility of the cadmium in the flue gas, and no great reduction of the treatment efficiency caused by the change of the particle size of the cadmium in the flue gas.
Description
Technical Field
The invention relates to the technical field of pollution purification, in particular to a treatment method of a membrane bioreactor for flue gas desulfurization/denitration/cadmium removal.
Background
The emission of nitrogen oxides in large quantities in the industrial production process in 2010 in China reaches 1852.4 ten thousand tons, wherein the emission of nitrogen oxides from industrial sources reaches 1465.6 ten thousand tons, and the occupation ratio reaches 79.1 percent, so that the nitrogen oxides are important causes of a series of environmental problems such as photochemical smog, acid rain and the like. In 2011, the emission amount of oxysulfide in China exceeds 2000 million tons, and the large amount of oxysulfide is discharged in the industrial production process to cause environmental problems such as acid rain and the like, damage to the lung and harm to the human body. Cadmium in the atmosphere has the characteristics of easy migration and easy biological enrichment.
The biological half-life period of cadmium can reach 10-30 years, which means that the emission of cadmium-containing flue gas can lead cadmium to continuously migrate, convert and enrich in an environmental medium, and biological amplification can occur along a food chain along with biological ingestion; cadmium is not an essential element for animals, plants and human bodies, shows obvious biotoxicity and causes great harm to human health and natural environment. As a first pollutant, in 2019, cadmium and compounds thereof are listed in "catalogue of toxic and harmful water pollutants" (first batch) by the ministry of ecological environment of the people's republic of China; the european union has made strict restrictions on the content of cadmium and its compounds in various products in the directive "restriction of the use of certain hazardous substances in electrical and electronic equipment". In 2016, the cadmium content of the flue gas discharged in the industrial production process of China reaches 1.12 multiplied by 102 tons, and the flue gas is derived from urban domestic garbage incineration flue gas, coal-fired power plant combustion flue gas, metal smelting flue gas and the like. In 2020, 1287 places exist for harmless treatment of domestic garbage, wherein in 463 places of domestic garbage incineration plants, the daily treatment capacity of the domestic garbage treated by the garbage incineration is 567804.44 tons, which accounts for 58.93 percent of the total treatment capacity.
Cadmium is used as an important chemical production raw material and exists in industrial products such as paper, metal products, glass products, plastics, kitchen garbage, rubber and the like, and cadmium-containing smoke is generated along with incineration of household garbage. Cadmium is taken as typical semi-volatile heavy metal and is volatilized in the incineration process, and part of the cadmium is condensed when the flue gas is cooled; cadmium and its compounds can volatilize at high temperature and simultaneously form metal vapor and submicron-sized particles with the particle size less than 1 mu m and even nano-sized particles.
According to the pollution control Standard for incineration of domestic waste (GB18485-2014) issued by the ministry of ecological environment, the emission concentration of cadmium and compounds thereof is limited to be below 0.1mg/m3, but in urban areas of China, the concentration of cadmium in the atmosphere is 12.9ng/m3 which is higher than the limit value of the air quality standard of China and the limit value of the world health organization. At present, cadmium in flue gas is treated by an adsorption method and a dust remover filtration and interception technology commonly used in industrial production, but the problems of low service life, high cost, secondary pollution of waste adsorbents and the like cannot be avoided; the dust remover has the defect of low efficiency of treating the smoke cadmium with small particle size. Compared with the biological method, the method has the advantages of no secondary pollution, low cost, environmental friendliness, easy management and the like, and has wide research and application prospects in the field of industrial waste gas treatment.
Disclosure of Invention
The invention aims to provide a membrane bioreactor treatment method for flue gas desulfurization/denitration/cadmium removal.
In order to solve the technical problems, the invention provides the following technical scheme:
a flue gas desulfurization/denitration/cadmium removal membrane bioreactor treatment method comprises the steps of introducing flue gas containing sulfur/nitrate/cadmium into a membrane bioreactor, and performing denitrification, desulfurization, bioadsorption and biostability on a biological membrane after mass transfer of a gas membrane in the membrane bioreactor to realize denitrification and desulfurization and simultaneously convert cadmium in the flue gas; wherein a biological membrane is formed in the membrane bioreactor in a growing way, and the biological membrane consists of one or more of Citrobacter, Desulfurovibrio and Pseudomonas.
The membrane bioreactor is connected with a circulating nutrient solution system, and the circulating nutrient solution system is used for spraying nutrient solution to assist the growth of one or more of Citrobacter, Desulfurovibrio and Pseudomonas on the biological membrane.
It should be noted that cadmium is converted into CdCO3 and CdS under the action of microorganisms, and the product can be recovered.
It is noted that the time for the flue gas to stay in the membrane bioreactor is 8-10 s.
Compared with physical treatment, the method has the advantages of low cost, conversion of the cadmium in the flue gas into a more stable form, reduction of the mobility of the cadmium in the flue gas, and no substantial reduction of the treatment efficiency caused by the change of the particle size of the cadmium in the flue gas. The product can be recovered by a certain means, and the resource utilization of cadmium is realized. The invention has the advantages of environmental friendliness and no risk of secondary pollution. Compared with the traditional biological purification device, the technology has the advantages of small occupied area, small device volume and lower investment cost. The membrane bioreactor technology has the advantages that the highest flue gas denitration efficiency can reach about 90 percent, the highest desulfurization efficiency can reach about 85 percent, the highest cadmium removal efficiency can reach about 95 percent, the total amount is higher than 85 percent under the operation of short retention time, and the membrane bioreactor technology has good stability of long-term operation, shows that the membrane bioreactor technology is suitable for the field of heavy metal waste gas treatment, and provides an innovative feasible idea with high efficiency and low energy consumption for the treatment of cadmium, nitrogen oxide and sulfur oxide in flue gas.
Drawings
FIG. 1 is a schematic diagram of an apparatus for carrying out the method of the present invention;
FIG. 2 is a graph of XRD analysis data of the conversion product in the membrane bioreactor of the present invention;
FIG. 3 is a three-dimensional fluorescence spectrum analysis chart of extracellular polymeric substances in the membrane bioreactor of the present invention;
FIG. 4 is a diagram of the morphological analysis of cadmium conversion products on a biofilm according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As a specific application of the invention, as shown in FIG. 1, the invention is a device of a membrane bioreactor treatment method, flue gas containing sulfur/nitrate/cadmium enters from a denitrification and desulfurisation membrane bioreactor 1, wherein the membrane bioreactor 1 is used for biofilm formation by microorganisms, a selected membrane material needs to have high temperature resistant flue gas characteristics, and the flue gas containing sulfur/nitrate/cadmium is purified and discharged after being reacted by the membrane bioreactor 1; in addition, in order to ensure the growth of the biological membrane of the membrane bioreactor, a circulating nutrient solution system 5 is also arranged, wherein a nutrient solution tank 4 and a water pump 3 spray nutrient solution to the membrane bioreactor 1, and a liquid flow meter 2 monitors and controls the spraying amount of the circulating nutrient solution.
The invention further relates to a treatment method of a membrane bioreactor for flue gas desulfurization/denitration/cadmium removal, which comprises the steps of introducing flue gas containing sulfur/nitrate/cadmium into the membrane bioreactor, and performing denitrification, desulfurization, bioadsorption and biostability on a biological membrane after mass transfer of the flue gas in the membrane bioreactor through a gas membrane to realize denitrification and desulfurization and simultaneously convert cadmium in the flue gas; wherein a biological membrane is formed in the membrane bioreactor in a growing way, and the composition of the biological membrane is one or more of Citrobacter, Desulfurovibrio and Pseudomonas.
The membrane bioreactor is connected with a circulating nutrient solution system, and the circulating nutrient solution system is used for spraying nutrient solution to assist the growth of one or more of Citrobacter, Desulfurovibrio and Pseudomonas on the biological membrane.
It is noted that cadmium is converted into CdCO3 and CdS by the action of microorganisms, and the product can be recovered.
It is noted that the time for the flue gas to stay in the membrane bioreactor is 8-10 s.
To further illustrate the effectiveness of the present invention, as shown in FIG. 2, XRD analysis of the conversion products in the membrane bioreactor shows that the cadmium in the flue gas is converted into CdCO by the action of denitrifying and denitrifying microorganisms in the membrane bioreactor3And a stable conversion product of CdS, wherein the formation of CdS results from a reverse sulfurization process, CdCO3To CO released by carbon metabolism occurring in denitrifying bacteria2The conversion process is free of electron transfer of cadmium.
As shown in fig. 2, the three-dimensional fluorescence spectrum analysis of extracellular polymeric substances in the membrane bioreactor shows that microorganisms on the biofilm can complex the cadmium in the flue gas by secreting extracellular polymeric substances to form a cadmium complex, so that the bioavailability of the cadmium in the flue gas is reduced, and the further conversion of the cadmium in the flue gas is facilitated.
As shown in FIG. 3, for morphological analysis of cadmium conversion products on a biological film, it is shown that flue gas cadmium is mainly converted into CdS with stable properties, and SE-Cd with the highest biological toxicity accounts for only 0.47%, which indicates that the technology can effectively stabilize flue gas cadmium on the basis of removing flue gas cadmium and is beneficial to the resource recovery of cadmium.
Example 1
Membrane bioreactor for treating cadmium and SOxAnd NOxThe urban domestic garbage incineration flue gas.
SO contained in the domestic garbage can be discharged in the incineration process2、SO3And the incineration flue gas of NO and cadmium is derived from sulfur, nitrogen and cadmium elements in rubber, plastics, paper and other substances. The membrane bioreactor is adopted to treat the waste incineration flue gas, and the SO content of more than 80 percent can be realized under the retention time of 8-10sxAnd NOxThe purification efficiency of cadmium is higher than 80%, the standard emission of the flue gas is realized, and the cadmium purification device has reliable operation performance.
Example 2
Membrane bioreactor for treating cadmium and SOxAnd NOxCoal-fired flue gas.
The boiler of the coal-fired power plant can release a large amount of SO in the combustion processx、NOxAnd the coal-fired flue gas containing Cd is derived from sulfur, nitrogen and cadmium elements in the coal powder, and the content of cadmium is relatively lower than that of the domestic garbage. The membrane bioreactor of denitrifying and denitrifying bacteria biofilm formation is adopted to treat the cadmium sulfide, the removal efficiency of nitrogen sulfur oxides can reach more than 70 percent, and the purification efficiency of cadmium can reach more than 90 percent. Compared with the traditional biological trickling filter device, the membrane bioreactor occupies less area, and saves the plant space.
Example 3
Membrane bioreactor for treating cadmium and SOxAnd NOxMetal smelting flue gas.
The SO content is generated in the smelting process of metal ore, particularly sulfur cadmium orex、NOxAnd cadmium, in which SOxAnd cadmium is derived from sulfur and cadmium elements in the sulfur-cadmium ore, NOxThermal nitrogen, fuel nitrogen, etc. from the smelting process. Treating metal smelting flue gas by using a denitrification and desulfurization membrane bioreactor to treat SOx、NOxAnd cadmium respectively reaches more than 80 percent, so that the target pollutants are effectively removed, and the operation cost is lower compared with that of the common physicochemical desulfurization and denitrification process.
Various modifications may be made by those skilled in the art based on the above teachings and concepts, and all such modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (4)
1. A flue gas desulfurization/denitration/cadmium removal membrane bioreactor treatment method is characterized in that the method comprises the steps of introducing flue gas containing sulfur/nitrate/cadmium into a membrane bioreactor, and performing denitrification, desulfurization, bioadsorption and biostability on a biological membrane after mass transfer of the flue gas through a gas membrane in the membrane bioreactor to realize denitrification and desulfurization and simultaneously convert cadmium in the flue gas; wherein a biological membrane is formed in the membrane bioreactor in a growing way, and the biological membrane consists of one or more of Citrobacter, Desulfurovibrio and Pseudomonas.
2. The membrane bioreactor processing method for flue gas desulfurization/denitrification/cadmium removal according to claim 1, wherein the membrane bioreactor is connected with a circulating nutrient solution system, and the circulating nutrient solution system is used for spraying nutrient solution to assist the growth of one or more of Citrobacter, Desulfurovibrio and Pseudomonas on the biofilm.
3. The membrane bioreactor processing method for flue gas desulfurization/denitration/cadmium removal according to claim 1, wherein cadmium is converted into CdCO3 and CdS by microorganism, and the products can be recovered.
4. The method of claim 1, wherein the time period for the flue gas to stay in the membrane bioreactor is 8-10 s.
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| CN111484146A (en) * | 2020-04-23 | 2020-08-04 | 金满塘(天津)生物科技有限公司 | Chelating agent for removing heavy metal pollution from water body and preparation method and application thereof |
| CN112495180A (en) * | 2020-11-26 | 2021-03-16 | 中山大学 | Thermophilic biological trickling filtration gas-liquid two-phase device and application thereof in removing heavy metals in flue gas |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949926A (en) * | 2012-11-16 | 2013-03-06 | 昆明理工大学 | Method for recycling sulfur dioxide (SO2) and heavy metal in metallurgical gas |
| CN109647179A (en) * | 2017-10-11 | 2019-04-19 | 中山大学 | A kind of Membrane Bioreactor for Wastewater Treatment method of denitrating flue gas demercuration |
| CN111484146A (en) * | 2020-04-23 | 2020-08-04 | 金满塘(天津)生物科技有限公司 | Chelating agent for removing heavy metal pollution from water body and preparation method and application thereof |
| CN112495180A (en) * | 2020-11-26 | 2021-03-16 | 中山大学 | Thermophilic biological trickling filtration gas-liquid two-phase device and application thereof in removing heavy metals in flue gas |
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