Biological deodorization filler as well as preparation method and application thereof

Abstract

The invention relates to the technical field of wastewater deodorization treatment, and discloses a biological deodorization filler, a preparation method and application thereof, the biological deodorization filler is composed of a porous polymer shell and deodorization particles filled in the porous polymer shell, the deodorization particles are composed of silicon dioxide porous hydrogel and anaerobic deodorization microorganisms colonized in pores of the silicon dioxide porous hydrogel, and the surfaces of the deodorization particles are provided with oxygen uptake slurry, and the anaerobic microorganisms colonized in the pores of the silicon dioxide porous hydrogel and the silicon dioxide porous hydrogel are arranged on the surfaces of the deodorization particles. The growth range of microorganisms is always in the shell, the problems that the microorganisms excessively grow to block the filler and are difficult to clean are avoided, the maintenance cost is reduced, and the treatment efficiency is improved.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater deodorization treatment, in particular to a biological deodorizing filler, a preparation method and application thereof. Background Art

[0002] Malodor is a gas that can damage the human living environment, produce unbearable odors or make people feel unpleasant. Malodor pollution not only affects people's health, but also destroys environmental harmony. Malodor substances have the characteristics of wide sources, large distribution range, and wide range of harm. For example, sewage treatment, sludge treatment, garbage composting, chemical pharmaceuticals, rubber plastics, printing and dyeing, fermentation pharmaceuticals, animal husbandry, etc. can all produce malodor sources.

[0003] At present, the deodorization technologies for sewage treatment mainly include activated carbon adsorption, thermal oxidation, ion method, chemical washing method, biological deodorization method, etc. Among them, the biological deodorization method has the characteristics of low energy consumption, environmental friendliness and low cost, and is currently a more commonly used odor treatment method. However, the biological deodorization method has a poor effect on the treatment of high-concentration odors. Therefore, those skilled in the art combine the biological deodorization method with the chemical washing method, treat the high-concentration odorous gas by chemical washing, and then use the biological deodorization method to treat the low-concentration odorous gas, such as a sewage treatment deodorization process disclosed in publication number CN118771585A, and another example is a restaurant kitchen waste odor purification treatment device disclosed in CN214598236U.

[0004] At present, the biological deodorization method mainly uses microorganisms to treat malodorous gases. In the prior art, a carrier loaded with microorganisms is usually used as a filler to treat malodorous gases. However, the applicant found that the microorganisms will still grow and multiply during the treatment process, which will cause the microbial colonies to quickly cover the filler and block the gaps in the filler. The deodorization efficiency is low and the filler needs to be replaced frequently. In addition, the overgrown microorganisms need to be removed during replacement, and the maintenance cost is high. Summary of the invention

[0005] In order to overcome the problems in the prior art that microorganisms in biological deodorizing fillers grow quickly and easily clog the fillers, reduce the deodorizing efficiency of the fillers, and increase the replacement and maintenance costs, the present invention provides a biological deodorizing filler, a preparation method and an application thereof. The biological deodorizing filler is composed of a porous polymer shell and deodorizing particles filled in the porous polymer shell. The deodorizing particles are composed of a silica porous hydrogel and anaerobic deodorizing microorganisms colonized in the pores of the silica porous hydrogel. The surface of the deodorizing particles is provided with an oxygen-absorbing slurry. The anaerobic microorganisms colonized in the pores of the silica porous hydrogel and arranged in the silica porous hydrogel make the growth range of the microorganisms always within the shell, thereby avoiding the problems of excessive growth of microorganisms clogging the filler and difficulty in cleaning, reducing maintenance costs and improving treatment efficiency.

[0006] The specific technical scheme of the present invention is: A biological deodorizing filler comprises a porous polymer shell and deodorizing particles arranged inside the porous polymer shell, wherein the deodorizing particles comprise a silica porous hydrogel and anaerobic deodorizing microorganisms colonized in the voids of the silica porous hydrogel, and an oxygen absorbing slurry is provided on the surface of the deodorizing particles, wherein the oxygen absorbing slurry is prepared by dispersing an oxygen absorber into a dispersant, and the slurry ratio of the oxygen absorbing slurry is 5 to 10:1.

[0007] The present invention provides a biological deodorizing filler, which is composed of a porous polymer shell and deodorizing particles arranged inside the porous polymer shell. The deodorizing particles are composed of porous silica hydrogel and anaerobic microorganisms colonized in the gaps of the silica hydrogel. An oxygen-absorbing slurry is also provided on the surface of the deodorizing particles. The biological deodorizing filler of the present application can decompose and absorb the malodorous gas generated in the sewage treatment process under an anaerobic environment.

[0008] The traditional biofilter is a liquid biological deodorization unit composed of microorganisms and fermentation liquid. The malodorous gas flows over the top of the biofilter and reacts with the fermentation liquid in the biofilter, thereby completing the function of removing the malodorous gas. However, the liquid form of the biofilter has a small effective treatment area and a low treatment efficiency. Therefore, in response to the above problems, the prior art treats the malodorous gas by means of solid microbial fillers. The solid microorganisms are loaded on a carrier, and the carrier is assembled in a packing tower for further treatment. The treatment area of ​​the solid microorganisms is significantly increased, and the treatment efficiency of the malodorous gas is significantly improved. During use, the present invention has found that when the solid microbial filler is used for a long time, the excessive growth of microorganisms will clog the gaps in the filler, resulting in a decrease in the treatment efficiency, and even causing the gas to be unable to effectively pass through the packing tower. In addition, the excessive growth of microorganisms will spread to the tower body, resulting in a significant decrease in the efficiency of tower maintenance and cleaning. Therefore, the present invention provides the above-mentioned biological deodorizing particles in view of the above-mentioned problems. The present invention uses silica porous hydrogel as a colonization carrier for microorganisms. The pore structure of the silica porous hydrogel provides growth space for the microorganisms. At the same time, the water in the hydrogel can be slowly released to ensure that the microorganisms can have a longer time effectiveness. The present invention also selects anaerobic microorganisms as deodorizing microorganisms, and arranges oxygen absorbers on the surface of the deodorizing particles to make the internal void structure of the deodorizing particles in an anaerobic state, thereby ensuring the effective reproduction of anaerobic microorganisms. Then, the deodorizing particles loaded with oxygen absorbers are filled into a porous polymer shell to form biological fillers. In addition, the biological fillers of the present invention can also limit the growth range of anaerobic microorganisms to the inside of the porous polymer shell at all times, and there will be no problem of excessive growth of microorganisms blocking the filler gaps. The biological deodorizing filler is easy to replace, and there is no need to clean the packing tower. When the gas in the packing tower cannot meet the emission requirements, it means that the filler has failed, and it only needs to be directly replaced with a new biological deodorizing filler.

[0009] Preferably, the pore size of the silica porous hydrogel is 20 to 50 μm.

[0010] Preferably, the oxygen absorbent is metal powder.

[0011] Preferably, the metal powder is one or more of iron, manganese, copper and platinum.

[0012] Preferably, the particle size of the metal powder is 50 to 200 nm.

[0013] Preferably, the anaerobic microorganisms are yeast, lactic acid bacteria, Bacillus subtilis, Acetobacter pasteurianus and photosynthetic bacteria.

[0014] A method for preparing the above-mentioned biological deodorant comprises the following steps: Step 1: dissolving tetraethyl orthosilicate in anhydrous ethanol and ultrasonically mixing to obtain a silicon precursor, stirring and mixing dodecylamine, anhydrous ethanol and water, adding the silicon precursor, continuing to stir and heat to react, adding ammonia water after heating to continue the reaction to obtain a crude product, and using anhydrous ethanol and water to elute and dry the crude product to obtain a porous silica hydrogel; Step 2: placing the silica porous hydrogel and anaerobic deodorizing microorganisms in a plant deodorizing fermentation solution for anaerobic fermentation to prepare a composite material, transferring the composite material into a spore culture solution for spore fermentation culture, separating the silica porous hydrogel and washing it to prepare deodorizing particles; Step 3: Place a porous polymer in a mold to form a porous polymer shell, disperse the oxygen absorber in water to form an oxygen absorber slurry, brush the oxygen absorber slurry on the surface of the deodorant particles, then fill the deodorant particles into the porous polymer shell, and seal the porous polymer shell to form a biological deodorant filler.

[0015] Preferably, in step 1, the volume ratio of tetraethyl orthosilicate to ammonia water is 1:3-5, and the mass ratio of tetraethyl orthosilicate to dodecylamine (0.57-1.425) is 1:0.2-0.5.

[0016] Preferably, the dispersant in step three is water.

[0017] An application of the above-mentioned biological deodorizing filler in sewage treatment includes the following steps: loading the above-mentioned biological deodorizing filler into a chemical leaching biological filtration deodorizing system, wherein the chemical leaching biological filtration deodorizing system includes an alkaline washing tank, an acid washing tank and a biological filtration tower which are connected in sequence.

[0018] Compared with the prior art, this application has the following technical effects: The present invention provides a biological deodorizing filler, a preparation method and an application thereof. The biological deodorizing filler consists of a porous polymer shell and deodorizing particles filled in the porous polymer shell. The deodorizing particles consist of a silica porous hydrogel and anaerobic deodorizing microorganisms colonized in the pores of the silica porous hydrogel. An oxygen absorbing slurry is provided on the surface of the deodorizing particles. The anaerobic microorganisms colonized in the pores of the silica porous hydrogel and arranged in the silica porous hydrogel make the growth range of the microorganisms always within the shell, thereby avoiding the problem of excessive growth of microorganisms clogging the filler and difficulty in cleaning, reducing maintenance costs and improving treatment efficiency. DETAILED DESCRIPTION

[0019] The present invention will be further described below in conjunction with the embodiments.

[0020] Embodiment 1: A biological deodorizing filler, the raw materials of which include a porous polymer shell and deodorizing particles arranged inside the porous polymer shell.

[0021] A method for preparing the above-mentioned biological deodorizing filler comprises the following steps: Step 1: Add 3 ml of tetraethyl orthosilicate to 35 ml of anhydrous ethanol and ultrasonically treat for 10 minutes to fully dissolve to prepare a silicon precursor, add 0.57 g of dodecylamine to the container, then add 30 ml of anhydrous ethanol and 53 ml of deionized water, stir at 1000 rpm for 2 minutes, then add the silicon precursor and mix thoroughly, after mixing evenly, place the container in a 45°C water bath and react at 300 rpm for 2 hours; then remove the container from the water bath, add 9 ml of ammonia water at room temperature to react for 2 hours to prepare a crude product, then use ethanol and water to centrifuge and wash the crude product 6 times, the centrifugal washing speed is 4000 rpm, the time is 5 minutes, dry at 60°C in a blast drying oven for 10 hours, and crush to a particle size of 100 mesh to prepare a porous silica hydrogel.

[0022] Step 2: Anaerobic fermentation of anaerobic microbial fermentation broth, plant extracts and silica porous hydrogel, anaerobic microbial fermentation broth and plant extracts using Chinese patent CN 05536509B discloses anaerobic microbial fermentation liquid and plant extract, the mass ratio of anaerobic microbial fermentation liquid, plant extract and silica porous hydrogel is 1:3:3, the anaerobic fermentation conditions are a rotation speed of 20r / min, and the fermentation time is 7 days; after the fermentation is completed, the silica porous hydrogel loaded with microorganisms is separated and transferred to a spore culture medium for spore fermentation culture, the mass ratio of the silica porous hydrogel loaded with microorganisms to the spore culture medium is 1:30, the spore culture medium is 20g / L glucose, 20g / L peptone, 20g / L yeast extract, 1g / L magnesium sulfate, 10g / L disodium hydrogen phosphate, 0.5g / L dibasic sodium phosphate, pH is 7, the conditions of spore fermentation culture are 35°C, 100r / min, and fermentation is 36h, after the fermentation is completed, the hydrogel is separated and cleaned to prepare deodorant particles.

[0023] Step 3: Disperse the oxygen absorber (iron powder, the particle size of the iron powder is 50-200nm) in water at a slurry ratio of 5-10:1 to prepare an oxygen absorbing slurry. After coating the oxygen absorbing slurry on the surface of the deodorizing particles, the deodorizing particles are filled in a porous polymer shell for packaging to prepare a biological deodorizing filler. The porous polymer shell is a PP spherical shell with a diameter of 1cm and a shell thickness of 3mm. A plurality of 0.1mm holes are provided on the surface of the shell.

[0024] An application of the above-mentioned biological deodorizing filler in sewage treatment comprises the following steps: The biological deodorizing filler is loaded into the biological filter tower of the chemical leaching biological filtration deodorizing system. The biological filtration deodorizing system also includes an acid washing tank connected to the biological filtration tower, an alkaline washing tank connected to the acid washing tank, and an odorous gas adsorption device connected to the alkaline washing tank. The biological deodorizing filler is filled in the filler layer of the biological filtration tower. The exhaust port of the biological filtration tower is provided with a detection device to detect the gas quality at the exhaust port, and determine whether the biological filler is invalid based on the gas quality.

[0025] Embodiment 2: A biological deodorizing filler, the raw materials of which include a porous polymer shell and deodorizing particles arranged inside the porous polymer shell.

[0026] A method for preparing the above-mentioned biological deodorizing filler comprises the following steps: Step 1: Add 3 ml of tetraethyl orthosilicate to 35 ml of anhydrous ethanol and ultrasonically treat for 10 minutes to fully dissolve to prepare a silicon precursor, add 1.0 g of dodecylamine to the container, then add 30 ml of anhydrous ethanol and 53 ml of deionized water, stir at 1000 rpm for 2 minutes, then add the silicon precursor and mix thoroughly, after mixing evenly, place the container in a 45°C water bath and react at 300 rpm for 2 hours; then remove the container from the water bath, add 12 ml of ammonia water at room temperature and react for 2 hours to prepare a crude product, then use ethanol and water to centrifuge and wash the crude product 6 times, the centrifugal washing speed is 4000 rpm, the time is 5 minutes, dry at 60°C in a blast drying oven for 10 hours, and crush to a particle size of 100 mesh to prepare a porous silica hydrogel.

[0027] Step 2: Anaerobic fermentation of anaerobic microbial fermentation broth, plant extracts and silica porous hydrogel, anaerobic microbial fermentation broth and plant extracts using Chinese patent CN 05536509B discloses anaerobic microbial fermentation liquid and plant extract, the mass ratio of anaerobic microbial fermentation liquid, plant extract and silica porous hydrogel is 1:3:3, the anaerobic fermentation conditions are a rotation speed of 20r / min, and the fermentation time is 7 days; after the fermentation is completed, the silica porous hydrogel loaded with microorganisms is separated and transferred to a spore culture medium for spore fermentation culture, the mass ratio of the silica porous hydrogel loaded with microorganisms to the spore culture medium is 1:30, the spore culture medium is 20g / L glucose, 20g / L peptone, 20g / L yeast extract, 1g / L magnesium sulfate, 10g / L disodium hydrogen phosphate, 0.5g / L dibasic sodium phosphate, pH is 7, the conditions of spore fermentation culture are 35°C, 100r / min, and fermentation is 36h, after the fermentation is completed, the hydrogel is separated and cleaned to prepare deodorant particles.

[0028] Step 3: Disperse the oxygen absorber (iron powder, the particle size of the iron powder is 50-200nm, copper powder, the particle size of the copper powder is 50-200nm) in water at a slurry ratio of 5-10:1 to prepare an oxygen absorbing slurry, coat the oxygen absorbing slurry on the surface of the above-mentioned deodorizing particles, and then fill the deodorizing particles into a porous polymer shell for packaging to prepare a biological deodorizing filler, wherein the porous polymer shell is a PP spherical shell with a diameter of 2cm and a shell thickness of 3mm, and a plurality of 0.1mm holes are provided on the surface of the shell.

[0029] An application of the above-mentioned biological deodorizing filler in sewage treatment comprises the following steps: The biological deodorizing filler is loaded into the biological filter tower of the chemical leaching biological filtration deodorizing system. The biological filtration deodorizing system also includes an acid washing tank connected to the biological filtration tower, an alkaline washing tank connected to the acid washing tank, and an odorous gas adsorption device connected to the alkaline washing tank. The biological deodorizing filler is filled in the filler layer of the biological filtration tower. The exhaust port of the biological filtration tower is provided with a detection device to detect the gas quality at the exhaust port, and determine whether the biological filler is invalid based on the gas quality.

[0030] Embodiment 3: A biological deodorizing filler, the raw materials of which include a porous polymer shell and deodorizing particles arranged inside the porous polymer shell.

[0031] A method for preparing the above-mentioned biological deodorizing filler comprises the following steps: Step 1: Add 3 ml of tetraethyl orthosilicate to 35 ml of anhydrous ethanol and ultrasonically treat for 10 minutes to fully dissolve to prepare a silicon precursor, add 1.4 g of dodecylamine to the container, then add 30 ml of anhydrous ethanol and 53 ml of deionized water, stir at 1000 rpm for 2 minutes, then add the silicon precursor and mix thoroughly, after mixing evenly, place the container in a 45°C water bath and react at 300 rpm for 2 hours; then remove the container from the water bath, add 15 ml of ammonia water at room temperature to react for 2 hours to prepare a crude product, then use ethanol and water to centrifuge and wash the crude product 6 times, the centrifugal washing speed is 4000 rpm, the time is 5 minutes, dry at 60°C in a blast drying oven for 10 hours, and crush to a particle size of 100 mesh to prepare a porous silica hydrogel.

[0032] Step 2: Anaerobic fermentation of anaerobic microbial fermentation broth, plant extracts and silica porous hydrogel, anaerobic microbial fermentation broth and plant extracts using Chinese patent CN 05536509B discloses anaerobic microbial fermentation liquid and plant extract, the mass ratio of anaerobic microbial fermentation liquid, plant extract and silica porous hydrogel is 1:3:3, the anaerobic fermentation conditions are a rotation speed of 20r / min, and the fermentation time is 7 days; after the fermentation is completed, the silica porous hydrogel loaded with microorganisms is separated and transferred to a spore culture medium for spore fermentation culture, the mass ratio of the silica porous hydrogel loaded with microorganisms to the spore culture medium is 1:30, the spore culture medium is 20g / L glucose, 20g / L peptone, 20g / L yeast extract, 1g / L magnesium sulfate, 10g / L disodium hydrogen phosphate, 0.5g / L dibasic sodium phosphate, pH is 7, the conditions of spore fermentation culture are 35°C, 100r / min, and fermentation is 36h, after the fermentation is completed, the hydrogel is separated and cleaned to prepare deodorant particles.

[0033] Step 3: Disperse the oxygen absorber (iron powder, the particle size of the iron powder is 50-200nm, manganese powder, the particle size of the iron powder is 50-200nm) in water at a slurry ratio of 5-10:1 to prepare an oxygen absorbing slurry, coat the oxygen absorbing slurry on the surface of the above-mentioned deodorizing particles, and then fill the deodorizing particles into a porous polymer shell for packaging to prepare a biological deodorizing filler, the porous polymer shell is a PP spherical shell with a diameter of 3cm, a shell thickness of 3mm, and a plurality of 0.1mm holes are set on the surface of the shell.

[0034] An application of the above-mentioned biological deodorizing filler in sewage treatment comprises the following steps: The biological deodorizing filler is loaded into the biological filter tower of the chemical leaching biological filtration deodorizing system. The biological filtration deodorizing system also includes an acid washing tank connected to the biological filtration tower, an alkaline washing tank connected to the acid washing tank, and an odorous gas adsorption device connected to the alkaline washing tank. The biological deodorizing filler is filled in the filler layer of the biological filtration tower. The exhaust port of the biological filtration tower is provided with a detection device to detect the gas quality at the exhaust port, and determine whether the biological filler is invalid based on the gas quality.

[0035] Comparative Example 1: Compared with Example 1, the biological filler in Comparative Example 1 adopts aerobic deodorizing microorganisms, and the other conditions are the same as those in Example 1.

[0036] Comparative Example 2: Compared with Example 1, no oxygen absorbent is provided in Comparative Example 2, and the other conditions are the same as those in Example 1.

[0037] Comparative Example 3: Compared with Example 1, in Comparative Example 3, no hydrogel or porous polymer shell was used for filling, and the other conditions were the same as those in Example 1.

[0038] Comparative Example 4: Compared with Example 1, the dosage of ammonia water and organic amine in Comparative Example 4 is too low; A method for preparing the above-mentioned biological deodorizing filler comprises the following steps: Step 1: Add 3 ml of tetraethyl orthosilicate to 35 ml of anhydrous ethanol and ultrasonically treat for 10 minutes to fully dissolve to prepare a silicon precursor, add 0.1 g of dodecylamine to the container, then add 30 ml of anhydrous ethanol and 53 ml of deionized water, stir at 1000 rpm for 2 minutes, then add the silicon precursor and mix thoroughly, after mixing evenly, place the container in a 45°C water bath and react at 300 rpm for 2 hours; then remove the container from the water bath, add 3 ml of ammonia water at room temperature and react for 2 hours to prepare a crude product, then use ethanol and water to centrifuge and wash the crude product 6 times, the centrifugal washing speed is 4000 rpm, the time is 5 minutes, dry at 60°C in a blast drying oven for 10 hours, and crush to a particle size of 100 mesh to prepare a porous silica hydrogel.

[0039] Step 2: Anaerobic fermentation of anaerobic microbial fermentation broth, plant extracts and silica porous hydrogel, anaerobic microbial fermentation broth and plant extracts using Chinese patent CN 05536509B discloses anaerobic microbial fermentation liquid and plant extract, the mass ratio of anaerobic microbial fermentation liquid, plant extract and silica porous hydrogel is 1:3:3, the anaerobic fermentation conditions are a rotation speed of 20r / min, and the fermentation time is 7 days; after the fermentation is completed, the silica porous hydrogel loaded with microorganisms is separated and transferred to a spore culture medium for spore fermentation culture, the mass ratio of the silica porous hydrogel loaded with microorganisms to the spore culture medium is 1:30, the spore culture medium is 20g / L glucose, 20g / L peptone, 20g / L yeast extract, 1g / L magnesium sulfate, 10g / L disodium hydrogen phosphate, 0.5g / L dibasic sodium phosphate, pH is 7, the conditions of spore fermentation culture are 35°C, 100r / min, and fermentation is 36h, after the fermentation is completed, the hydrogel is separated and cleaned to prepare deodorant particles.

[0040] Step 3: Disperse the oxygen absorber (iron powder, the particle size of the iron powder is 50-200nm) in water at a slurry ratio of 5-10:1 to prepare an oxygen absorbing slurry. After coating the oxygen absorbing slurry on the surface of the above-mentioned deodorizing particles, the deodorizing particles are filled in a porous polymer shell for packaging to prepare a biological deodorizing filler. The porous polymer shell is a PP spherical shell with a diameter of 3cm and a shell thickness of 3mm. The shell surface is provided with a hole with a diameter of 0.1mm.

[0041] Comparative Example 5: Compared with Example 1, the dosage of ammonia water and organic amine in Comparative Example 5 is too high; A method for preparing the above-mentioned biological deodorizing filler comprises the following steps: Step 1: Add 3 ml of tetraethyl orthosilicate to 35 ml of anhydrous ethanol and ultrasonically treat for 10 minutes to fully dissolve to prepare a silicon precursor, add 2.0 g of dodecylamine to the container, then add 30 ml of anhydrous ethanol and 53 ml of deionized water, stir at 1000 rpm for 2 minutes, then add the silicon precursor and mix thoroughly, after mixing evenly, place the container in a 45°C water bath and react at 300 rpm for 2 hours; then remove the container from the water bath, add 20 ml of ammonia water at room temperature and react for 2 hours to prepare a crude product, then use ethanol and water to centrifuge and wash the crude product 6 times, the centrifugal washing speed is 4000 rpm, the time is 5 minutes, dry at 60°C in a blast drying oven for 10 hours, and crush to a particle size of 100 mesh to prepare a porous silica hydrogel.

[0042] Step 2: Anaerobic fermentation of anaerobic microbial fermentation broth, plant extracts and silica porous hydrogel, anaerobic microbial fermentation broth and plant extracts using Chinese patent CN 05536509B discloses anaerobic microbial fermentation liquid and plant extract, the mass ratio of anaerobic microbial fermentation liquid, plant extract and silica porous hydrogel is 1:3:3, the anaerobic fermentation conditions are a rotation speed of 20r / min, and the fermentation time is 7 days; after the fermentation is completed, the silica porous hydrogel loaded with microorganisms is separated and transferred to a spore culture medium for spore fermentation culture, the mass ratio of the silica porous hydrogel loaded with microorganisms to the spore culture medium is 1:30, the spore culture medium is 20g / L glucose, 20g / L peptone, 20g / L yeast extract, 1g / L magnesium sulfate, 10g / L disodium hydrogen phosphate, 0.5g / L dibasic sodium phosphate, pH is 7, the conditions of spore fermentation culture are 35°C, 100r / min, and fermentation is 36h, after the fermentation is completed, the hydrogel is separated and cleaned to prepare deodorant particles.

[0043] Step 3: Disperse the oxygen absorber (iron powder, the particle size of the iron powder is 50-200nm) in water at a slurry ratio of 5-10:1 to prepare an oxygen absorbing slurry. After coating the oxygen absorbing slurry on the surface of the above-mentioned deodorizing particles, the deodorizing particles are filled in a porous polymer shell for packaging to prepare a biological deodorizing filler. The porous polymer shell is a PP spherical shell with a diameter of 3cm and a shell thickness of 3mm. The shell surface is provided with a hole with a diameter of 0.1mm.

[0044] Test example 1: The deodorization performance of the biological deodorization fillers prepared in Examples 1 to 3 and Comparative Examples 1 and 5 was tested. The deodorization performance items included: ammonia removal rate, hydrogen sulfide removal rate, and biological filler service life. The biofilter towers filled with biological deodorizing fillers in Examples 1 to 3 were tested using malodorous gases. The filler layer of the biofilter tower was 5m 3 , the ammonia content in the odorous gas is 5mg / m 3 , trimethylamine content is 0.8mg / m 3 , hydrogen sulfide content is 0.6mg / m 3 , the content of methyl mercaptan is 0.035mg / m 3 , the content of methyl sulfide is 1.1mg / m 3 , the content of dimethyl disulfide is 0.71mg / m 3 , the content of carbon disulfide is 10mg / m 3 , the content of styrene is 19mg / m 3 .

[0045] The ammonia removal rate was measured by Nessler's reagent spectrophotometry to test the ammonia content in the malodorous gas before entering the biofilter tower and the ammonia content at the outlet of the biofilter tower. Ammonia removal rate = (ammonia content in the gas before treatment - ammonia content in the gas after treatment) / ammonia content before treatment.

[0046] The hydrogen sulfide removal rate was determined by using methylene blue spectrophotometry to test the hydrogen sulfide content in the malodorous gas before entering the biofilter tower and the hydrogen sulfide content at the outlet of the biofilter tower. The hydrogen sulfide removal rate = (hydrogen sulfide content in the gas before treatment - hydrogen sulfide content in the gas after treatment).

[0047] The service life of biological deodorizing filler is tested according to the test standard of GB14554-93 Emission Standard of Malodorous Pollutants. The malodorous gas is treated by a biological filter tower, and the treatment time of the biological filter tower is recorded. If the malodorous substance content of the gas at the discharge port of the biological filter tower exceeds the minimum emission standard, it is the service life of the biological deodorizing filler. The minimum emission standard is an ammonia content of 1 mg / m 3 , trimethylamine content is 0.05mg / m 3 , hydrogen sulfide content is 0.03mg / m 3 , the content of methyl mercaptan is 0.004mg / m 3 , the content of methyl sulfide is 0.03mg / m 3 , the content of dimethyl disulfide is 0.03mg / m 3 , the content of carbon disulfide is 2mg / m 3 , the content of styrene is 3mg / m 3 .

[0048] The test results are shown in Table 1; Table 1 Antibacterial properties of mildew inhibitors Ammonia removal rate (%) Hydrogen sulfide removal rate (%) Biological deodorizing filler service life (d) Example 1 99.5 99.3 15 Example 2 99.1 99.2 17 Example 3 99.3 99.4 15 Comparative Example 1 / / / Comparative Example 2 / / / Comparative Example 3 / / / Comparative Example 4 68.8 72.3 / Comparative Example 5 75.3 76.1 / As shown in Table 1, the ammonia removal rate of the biological packing tower of Examples 1 to 3 can reach 99.1-99.5%, and the hydrogen sulfide removal rate can reach 99.2-99.4%, which has excellent removal effect on hydrogen and hydrogen sulfide. In addition, it can be seen from the service life of the deodorizing packing that the service life of the biological filter tower after continuous malodorous gas treatment is 15-17 days, and the service life is long. The preparation process of the biological packing of the present invention is simple. After the biological deodorizing packing fails, it only needs to be quickly filled with new packing, and there is no need to clean the filter tower, so the maintenance cost is low.

[0049] In Comparative Example 1, aerobic microorganisms were used as deodorizing microorganisms. It was found that aerobic microorganisms could not grow and reproduce in the deodorizing particles, resulting in the inability of the biological deodorizing filler to deodorize.

[0050] In Comparative Example 2, the surface of the porous silica hydrogel was not loaded with an oxygen absorber. It was found that the anaerobic microorganisms in the deodorizing particles could not reproduce and grow, resulting in the inability of the biological deodorizing filler to deodorize.

[0051] In Comparative Example 3, no porous polymer shell is provided outside the deodorant particles. It is found that the deodorant particles are relatively soft in texture and will be directly stacked into a whole after being directly filled in the filler layer. At the same time, the large stacking volume causes the lower hydrogel to be compacted, making it difficult for the gas to enter the pores of the hydrogel, and the malodorous gas cannot be effectively treated. The porous polymer shell of the present application can separate the silica hydrogel into small microbial reaction units, thereby increasing the surface area for microbial treatment. At the same time, the porous polymer shell can prevent the problem of stacking and compaction caused by the excessive volume of the silica porous hydrogel.

[0052] In Comparative Examples 4 and 5, the dosage of organic amines and ammonia water was investigated respectively. Organic amines and ammonia water can regulate the porosity and pore size of the porous silica hydrogel. In Comparative Example 4, too low organic amines and ammonia water were used. It was found that the porosity and pore size of the porous silica hydrogel formed were small, resulting in a significant reduction in the number of loaded microorganisms, thereby resulting in a significant reduction in the deodorization performance. In addition, when excessive organic amines and ammonia were used to treat the silica hydrogel in Comparative Example 5, although the porosity increased, when the pore size was too large, some microorganisms would leave the pores of the porous silica hydrogel during the treatment process, reducing the colonization effect of microorganisms in the silica multi-purpose hydrogel, thereby reducing the deodorization effect of the deodorizing particles.

[0053] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A biological deodorizing filler, characterized in that: The invention comprises a porous polymer shell and deodorizing particles arranged inside the porous polymer shell, wherein the deodorizing particles comprise a porous silica hydrogel and anaerobic deodorizing microorganisms colonized in the voids of the porous silica hydrogel, and the surface of the deodorizing particles is provided with an oxygen absorbing slurry, wherein the oxygen absorbing slurry is prepared by dispersing an oxygen absorber into a dispersant, and the slurry ratio of the oxygen absorbing slurry is 5-10:

1.

2. The biological deodorizing filler according to claim 1, characterized in that: The pore size of the silica porous hydrogel is 20-50 μm.

3. The biological deodorizing filler according to claim 1, characterized in that: The oxygen absorbent is metal powder.

4. The biological deodorizing filler according to claim 3, characterized in that: The metal powder is one or more of iron, manganese, copper and platinum.

5. The biological deodorizing filler according to claim 3 or 4, characterized in that: The particle size of the metal powder is 50-200 nm.

6. The biological deodorizing filler according to claim 1, characterized in that: The anaerobic microorganisms are yeast, lactic acid bacteria, Bacillus subtilis, Acetobacter pasteurianus and photosynthetic bacteria.

7. A method for preparing the biological deodorizing filler according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1: using tetraethyl orthosilicate, dodecylamine and ammonia water as raw materials to prepare a porous silica hydrogel; Step 2: subjecting the silica porous hydrogel and anaerobic deodorizing microorganisms to anaerobic fermentation to prepare a composite material, and then subjecting the composite material to spore-forming fermentation culture to prepare deodorizing particles; Step 3: placing a porous polymer in a mold to form a porous polymer shell, dispersing an oxygen absorber in a dispersant to form an oxygen absorber slurry, brushing the oxygen absorber slurry on the surface of deodorant particles, and then filling the deodorant particles into the porous polymer shell and sealing it to form a biological deodorant filler.

8. The preparation method according to claim 7, characterized in that: The volume ratio of tetraethyl orthosilicate to ammonia water is 1:3-5, and the mass ratio of tetraethyl orthosilicate to dodecylamine is 1:0.2-0.

5.

9. The preparation method according to claim 7, characterized in that: The dispersant is water.

10. An application of the biological deodorizing filler according to any one of claims 1 to 7 in wastewater treatment, characterized in that: The method comprises the following steps: loading the biological deodorizing filler into the chemical leaching biological filtration deodorizing system, wherein the chemical leaching biological filtration deodorizing system comprises an alkaline washing tank, an acid washing tank and a biological filtration tower which are connected in sequence, and the biological deodorizing filler is the biological deodorizing filler as described in any one of claims 1 to 7.