Metal-organic framework-based bio-trickling filter filler, preparation method and application thereof

Abstract

The application discloses a kind of metal organic framework-based biological trickling filter fillings, including soluble metal salt, organic ligand and binder.It also includes preparation method, including soluble metal salt is mixed with organic ligand in solvent, heating reaction, obtain metal organic framework material;Metal organic framework material is mixed with binder granulation, obtain metal organic framework-based biological trickling filter fillings.The preparation method of the biological trickling filter fillings is simple, structural performance is stable, with great specific surface area and strong biological adsorption capacity, sulfur-containing malodorous waste gas has very good adsorption effect at the same time, degradation efficiency is higher, can effectively make adsorption method and biological method be combined, and play the advantages of two, compared with prior art, the removal rate of hydrogen sulfide, organic sulfide, benzene series in sulfur-containing malodorous waste gas can reach 99.5% in the application.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of environmental protection and purification, and particularly relates to a biological trickling filter filler based on a metal organic framework, a preparation method and application thereof. BACKGROUND

[0002] The sewage treatment field of a petrochemical enterprise is one of main pollution sources of malodor pollution. A large amount of malodor waste gas is generated in the process of oil refining, part of which is discharged into the atmosphere through running, leaking and the like, and most of the malodor substances are water-miscible and finally enter the sewage treatment field with sewage. The main components of these malodor pollution sources are H2S, organic sulfide, ammonia, organic acid, benzene series and the like. With the attention of people to the malodor pollution problem, various treatment methods have emerged, mainly including combustion method, oxidation method, absorption method, adsorption method, biological method and the like. The physical and chemical treatment methods have problems such as large investment, complex operation, high operation cost, easy secondary pollution and the like. The biological deodorization method has become the main method for deodorization in recent years due to the characteristics of less investment, low operation cost, reliable performance, easy management, good treatment effect and less secondary pollution.

[0003] The biological treatment of malodor waste gas is the most economical and effective method. The biological purification method of malodor waste gas includes a biological absorption tank, a biological washing tank, a biological trickling filter tower and a biological filtration tank, and has good treatment effect and convenient operation. The biological trickling filter tower mainly comprises a filler tower with one or more layers of fillers. The surface of the fillers is covered with a biological membrane of several millimeters thick formed by microorganisms. Liquid containing soluble inorganic domesticated nutrients is uniformly sprayed on the fillers from the top of the tower. The liquid flows downward from the top to the bottom and is then discharged from the bottom and recycled. Malodor waste gas enters the biological trickling filter tower from the bottom, is purified by contacting with the wet biological membrane during the rising process, and is discharged from the top of the tower.

[0004] People have developed various filtration fillers capable of attaching various microorganisms, such as compost, slag, activated carbon, zeolite, peat, plastic and synthetic resin and the like. The fillers can provide a habitat for a variety of microorganisms to grow and form a stable ecological community. The surface of the fillers is covered with a biological membrane, which increases the biomass and thus improves the efficiency of odor treatment and the utilization rate of oxygen. The filler is the core component of devices such as biological filtration, biological trickling filtration and biological fluidized bed. It is not only a support carrier for biological growth, but also a mass transfer medium for gas-liquid two-phase, and its performance directly affects the deodorization treatment effect.

[0005] Metal Organic Frameworks (MOFs) as a new type of porous material, composed of a variety of metal centers and a variety of organic ligands, has adjustable structure, and is widely used in gas adsorption, separation, catalysis, energy and radiation detection. MOFs are used for adsorption method to treat organic waste gas, and have certain application prospect in the field of organic waste gas adsorption due to their high specific surface area, good stability and structural variability. Dong Xiaojun et al. recorded in the Journal of Shandong Jianzhu University, Vol. 38 (No. 2), pp. 87-91 that MOFs materials were used to treat acid gas with good effect.

[0006] Adsorption method is a simple and direct method with obvious adsorption effect, but the high cost, secondary pollution and low recycling hinder its development. Therefore, finding an economical and sustainable method has become a hot research topic at home and abroad. Biological method has the advantages of economy, environmental protection and sustainability, and attracts people's attention. If microorganisms are directly used to degrade malodorous waste gas, the degradation time is long, the treatment efficiency is low, and high concentration of malodorous waste gas will also affect the microorganisms. Therefore, the use of microorganisms alone is limited in actual practice.

[0007] In patent application No. 202011388437.9, a spray liquid for waste gas and odor purification and a preparation method thereof are described, which adds metal organic framework material to the spray liquid, uses metal organic framework material with high pore volume to adsorb pollutants in waste gas and odor, and increases the capture rate of hydrophobic substances. This method only uses metal organic framework with photocatalytic performance to adsorb pollutants, without adding microorganisms.

[0008] Therefore, it is urgent to develop a new type of biological deodorization filler which has good adsorption effect on sulfur-containing malodorous waste gas, high degradation efficiency, can effectively combine adsorption method and biological method, and play the advantages of both. Therefore, it is of great significance to introduce MOFs material into the biological trickling filter filler system. SUMMARY

[0009] The purpose of the present application is to provide a biological trickling filter filler based on metal organic framework, a preparation method and applications thereof, to solve the problems raised in the background art.

[0010] To achieve the above-mentioned purpose, the present application provides the following technical solution: a biological trickling filter filler based on metal organic framework, comprising

[0011] Soluble metal salt, organic ligand and binder.

[0012] Preferably, the soluble metal salt comprises a combination of one or more of lead nitrate, silver nitrate, barium nitrate, bismuth nitrate, calcium nitrate, chromium nitrate, copper nitrate, copper acetate, zinc nitrate, zinc acetate.

[0013] Preferably in any of the above solutions, the organic ligand comprises a combination of one or more of trimesic acid, terephthalic acid, 3,5-pyridinedicarboxylic acid, 2,5-dimethyl terephthalic acid, 5-hydroxyisophthalic acid.

[0014] Preferably in any of the above solutions, the binder comprises a combination of one or more of hydroxymethyl cellulose, chitosan, polyurethane, sodium alginate.

[0015] A method for preparing a metal-organic framework-based bio-trickling filter filler, comprising the following steps:

[0016] S11: mixing a soluble metal salt and an organic ligand in a solvent according to a molar ratio of 1:0.1-5, heating and reacting to obtain a metal-organic framework material;

[0017] S12: mixing the metal-organic framework material and a binder according to a mass ratio of 1:0.1-2 to granulate, to obtain a metal-organic framework-based bio-trickling filter filler.

[0018] Preferably in any of the above solutions, the solvent comprises a combination of one or more of N,N dimethylformamide, N,N dimethylacetamide, ethanol and water.

[0019] Preferably in any of the above solutions, the binder comprises a combination of one or more of hydroxymethyl cellulose, chitosan, polyurethane, sodium alginate.

[0020] Preferably in any of the above solutions, in step S1, the reaction temperature is 100-200°C, and the reaction time is 12-72h.

[0021] An application of a metal-organic framework-based bio-trickling filter filler in treatment of sulfur-containing malodorous waste gas, comprising the following steps:

[0022] S21: loading a microbial flora onto the surface of the metal-organic framework-based bio-trickling filter filler to obtain a metal-organic framework filler loaded with a microbial flora;

[0023] S22: loading the metal-organic framework filler loaded with the microbial flora into a bio-trickling tower;

[0024] S23: performing a spraying operation at the top of the bio-trickling tower using a spraying liquid, the spraying liquid flowing through the metal-organic framework filler loaded with the microbial flora and dropping to the bottom of the bio-trickling tower;

[0025] S24, the sulfur-containing malodorous waste gas is introduced into the bottom of the biological trickling tower, and is used to make the sulfur-containing malodorous waste gas pass through the metal organic framework filler loaded with the microbial flora, and the purified gas is discharged from the top of the tower;

[0026] S25: collect the spray liquid at the bottom of the biological trickling tower, and discharge it, and recycle it as spray water after biochemical treatment.

[0027] Preferably in any of the above solutions, in step S21, the preparation method of the metal organic framework filler loaded with the microbial flora comprises:

[0028] S211: the metal organic framework-based biological trickling filler is activated by N-hydroxy succinimide and N(3-dimethylaminopropyl)N'-ethyl carbodiimide hydrochloride;

[0029] S212: then the microorganism and the activated metal organic framework-based biological trickling filler are dispersed in PBS buffer to obtain the metal organic framework filler loaded with the microbial flora.

[0030] Preferably in any of the above solutions, the biological trickling tower comprises a tower body, a sprayer arranged at the upper part of the tower body, a metal organic framework filler arranged at the middle part of the tower body, a gas distributor arranged at the lower part of the tower body, and a gas inlet arranged at the bottom of the tower body, the bottom of the tower body is a spray liquid storage tank, and a liquid discharge port is arranged on the spray liquid storage tank.

[0031] Preferably in any of the above solutions, the spray liquid is an aqueous solution containing inorganic nutrient salt, and is intermittently sprayed at a fixed time to maintain the bed moisture content at 65%-80%.

[0032] Preferably in any of the above solutions, the microbial flora is a composite microbial flora for purifying sulfur-containing malodorous waste gas, and the biological activity temperature of the microbial flora is 20-45 DEG C.

[0033] The sulfur-containing malodorous waste gas mainly refers to malodorous waste gas discharged by a sewage treatment facility of a petrochemical enterprise, and has the characteristics of low concentration and large air volume, wherein the mass concentration of hydrogen sulfide is 10-200 mg / m3, the mass concentration of volatile organic sulfides (C1-C3 thiol and sulfide, dimethyl disulfide, etc.) is 50-500 mg / m3, and the mass concentration of benzene series (benzene, toluene, xylene, etc.) is 100-2000 mg / m3.

[0034] The technical effects and advantages of the present application are as follows: based on the metal organic framework material (MOF), the MOF material with excellent performance is synthesized by selecting the metal center and the organic ligand, the biological trickling filler is made in the form of granulation, and the microbial flora is loaded to make it suitable for the treatment process of the sulfur-containing malodorous waste gas.

[0035] The preparation method of the biological trickling filter filler is simple, the structural performance is stable, the specific surface area is large, the biological adsorption capacity is strong, the sulfur-containing malodorous waste gas has a good adsorption effect, the degradation efficiency is high, the adsorption method and the biological method can be effectively combined, and the advantages of the two methods can be played. Compared with the prior art, the removal rates of hydrogen sulfide, organic sulfides and benzene series in the sulfur-containing malodorous waste gas can reach 99.5%. DETAILED DESCRIPTION

[0036] The specific embodiments of the present application will be further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0037] Example 1

[0038] (1) The present embodiment provides a preparation method of a metal organic framework-based biological trickling filter filler, comprising the following steps: 0.15 mol of barium nitrate and 0.1 mmol of 3,5-pyridine dicarboxylic acid are dissolved in 100 ml of deionized water and N,N dimethylformamide, and stirring is performed to obtain a suspension, the suspension is heated in a drying box at 150°C for 24h to obtain a metal organic framework material (MOF), then the MOF is granulated with a binder (hydroxymethyl cellulose) according to a certain mass ratio (MOF:binder=2:1), 150 mL of water is added for mixing and shaping at the same time, the obtained mixture is granulated and freeze-dried to obtain the metal organic framework-based biological trickling filter filler.

[0039] (2) The preparation process of the metal organic framework filler loaded with microbial flora comprises the following steps: 0.1 mol of N-hydroxysuccinimide (NHS), 0.1 mol of N(3-dimethylaminopropyl)N'-ethylcarbodiimide hydrochloride (EDC) and 5 g of dried metal organic framework filler are dispersed in 500 mL of citrate buffer solution pH 6.0, stirring is performed at room temperature for 24h for activation, the odor waste gas purification special domesticated composite microbial flora is centrifuged after being expanded in a liquid culture medium, the bacterial bodies and the activated metal organic framework filler are dispersed in PBS buffer solution, and are placed in a constant-temperature shaking bed under the condition of 35°C and 250 rpm for 24h, the carboxyl functional groups on the upper surface are connected to the amino groups on the surface of the bacteria through chemical bonds, and the bacterial bodies are firmly loaded on the surface of the material.

[0040] (3) The prepared metal organic framework filler loaded with microbial flora was packed into a bio-trickling tower for treatment of sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 50 mg / m3, the mass concentration of volatile organic sulfide was 100 mg / m3, and the mass concentration of benzene series was 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 100%, 100% and 99.9%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 200 mg / m3, the mass concentration of volatile organic sulfide was 500 mg / m3, and the mass concentration of benzene series was 2000 mg / m3.

[0041] The removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 100%, 99.9% and 99.8%, respectively.

[0042] Example 2:

[0043] (1) The present embodiment provides a preparation method of a bio-trickling filler based on metal organic framework, comprising the following steps: 0.1 mol of barium nitrate and 0.1 mmol of terephthalic acid are dissolved in 100 ml of deionized water, and stirring is performed to obtain a suspension, the suspension is heated in a drying box at 150°C for 36 h to obtain a metal organic framework material (MOF), then the MOF is granulated with a binder (polyurethane) at a certain mass ratio (MOF: binder = 3: 1), and 150 mL of water is added for mixing and shaping, the obtained mixture is granulated and freeze-dried to obtain a bio-trickling filler based on metal organic framework.

[0044] (2) The preparation process of the metal organic framework filler loaded with microbial flora is the same as that of Example 1.

[0045] (3) The prepared metal organic framework filler loaded with microbial flora was packed into a bio-trickling tower for treatment of sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 50 mg / m3, the mass concentration of volatile organic sulfide was 100 mg / m3, and the mass concentration of benzene series was 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 100%, 99.8% and 99.9%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 200 mg / m3, the mass concentration of volatile organic sulfide was 500 mg / m3, and the mass concentration of benzene series was 2000 mg / m3.

[0046] The removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 99.9%, 99.7% and 99.8%, respectively.

[0047] Example 3:

[0048] (1) The embodiment provides a preparation method of a metal organic framework-based biological trickling filter filler, comprising the following steps: 0.1 mol of chromium nitrate and 0.1 mmol of m-benzenetricarboxylic acid are dissolved in 100 ml of N,N-dimethylacetamide, and stirring is performed to obtain a suspension, the suspension is heated at 180 DEG C in a drying box for 36 h to obtain a metal organic framework material (MOF). Then the MOF is granulated with a binder (sodium alginate) at a certain mass ratio (MOF:binder = 1:1), 150 mL of water is added for mixing and shaping at the same time, the obtained mixture is granulated and freeze-dried to obtain the metal organic framework-based biological trickling filter filler.

[0049] (2) The preparation process of the metal organic framework filler loaded with a microbial flora is the same as that in embodiment 1.

[0050] (3) The prepared metal organic framework filler loaded with a microbial flora is filled into a biological trickling filter tower to perform a treatment experiment on sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 50 mg / m3, the mass concentration of volatile organic sulfides is 100 mg / m3, and the mass concentration of benzene series is 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfides and benzene series in the sulfur-containing malodorous waste gas are 100%, 99.9% and 99.9% respectively in the embodiment; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 200 mg / m3, the mass concentration of volatile organic sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

[0051] The removal rates of hydrogen sulfide, organic sulfides and benzene series in the sulfur-containing malodorous waste gas are 100%, 99.8% and 99.7% respectively in the embodiment.

[0052] Embodiment 4:

[0053] (1) The embodiment provides a preparation method of a metal organic framework-based biological trickling filter filler, comprising the following steps: 0.2 mol of copper acetate and 0.1 mmol of 5-hydroxyisophthalic acid are dissolved in 100 ml of deionized water and N,N-dimethylacetamide, and stirring is performed to obtain a suspension, the suspension is heated at 120 DEG C in a drying box for 48 h to obtain a metal organic framework material (MOF). Then the MOF is granulated with a binder (chitosan) at a certain mass ratio (MOF:binder = 1:1), 150 mL of water is added for mixing and shaping at the same time, the obtained mixture is granulated and freeze-dried to obtain the metal organic framework-based biological trickling filter filler.

[0054] (2) The preparation process of the metal organic framework filler loaded with a microbial flora is the same as that in embodiment 1.

[0055] (3) The prepared metal organic framework filler loaded with microbial flora was packed into a biological trickling filter tower to perform a treatment experiment on sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 50 mg / m3, the mass concentration of volatile organic sulfide was 100 mg / m3, and the mass concentration of benzene series was 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 99.9%, 99.8% and 99.8%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 200 mg / m3, the mass concentration of volatile organic sulfide was 500 mg / m3, and the mass concentration of benzene series was 2000 mg / m3.

[0056] The removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 99.8%, 99.6% and 99.7%, respectively.

[0057] Example 5:

[0058] (1) The present embodiment provides a preparation method of a metal organic framework-based biological trickling filter filler, comprising the following steps: dissolving 0.15 mol of zinc nitrate and 0.1 mmol of 2,5-dimethyl terephthalic acid in 100 ml of ethanol and N,N dimethylformamide, stirring to obtain a suspension, heating the suspension in a drying box at 120°C for 36 h to obtain a metal organic framework material (MOF), then granulating the MOF with a binder (sodium alginate) at a certain mass ratio (MOF:binder = 1:1), while adding 150 mL of water for mixing and shaping, and freeze-drying the obtained mixture to obtain a metal organic framework-based biological trickling filter filler.

[0059] (2) The preparation process of the metal organic framework filler loaded with microbial flora is the same as that in Example 1.

[0060] (3) The prepared metal organic framework filler loaded with microbial flora was packed into a biological trickling filter tower to perform a treatment experiment on sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 50 mg / m3, the mass concentration of volatile organic sulfide was 100 mg / m3, and the mass concentration of benzene series was 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 99.8%, 99.7% and 99.8%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas was 200 mg / m3, the mass concentration of volatile organic sulfide was 500 mg / m3, and the mass concentration of benzene series was 2000 mg / m3.

[0061] The removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas were 99.6%, 99.5% and 99.7%, respectively.

[0062] Example 6:

[0063] (1) The present embodiment provides a preparation method of a metal organic framework-based bio-trickling filter filler, comprising the following steps: dissolving 0.15 mol of lead nitrate and 0.1 mmol of trimesic acid in 100 ml of deionized water, stirring to obtain a suspension, heating the suspension in a drying oven at 150°C for 18 h to obtain a metal organic framework material (MOF), then granulating the MOF with a binder (hydroxymethyl cellulose) according to a certain mass ratio (MOF: binder = 2:1), while adding 150 mL of water for mixing and shaping, and freeze-drying the obtained mixture to obtain a metal organic framework-based bio-trickling filter filler.

[0064] (2) The preparation process of the metal organic framework filler loaded with microbial flora is the same as that of Example 1.

[0065] (3) The prepared metal organic framework filler loaded with microbial flora is packed into a bio-trickling filter tower to perform a treatment experiment of sulfur-containing malodorous waste gas: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 50 mg / m3, the mass concentration of volatile organic sulfide is 100 mg / m3, and the mass concentration of benzene series is 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide, and benzene series in the sulfur-containing malodorous waste gas in the present embodiment are 99.7%, 99.8%, and 99.9%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 200 mg / m3, the mass concentration of volatile organic sulfide is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

[0066] The removal rates of hydrogen sulfide, organic sulfide, and benzene series in the sulfur-containing malodorous waste gas in the present embodiment are 99.5%, 99.7%, and 99.6%, respectively.

[0067] Comparative Example 1:

[0068] The traditional filler: The traditional filler of the bio-trickling filter tower is ceramsite, and the particle size is 3-6 mm.

[0069] A treatment experiment of sulfur-containing malodorous waste gas is performed: when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 50 mg / m3, the mass concentration of volatile organic sulfide is 100 mg / m3, and the mass concentration of benzene series is 500 mg / m3, the removal rates of hydrogen sulfide, organic sulfide, and benzene series in the sulfur-containing malodorous waste gas in the present embodiment are 93.2%, 81.4%, and 87.5%, respectively; when the mass concentration of hydrogen sulfide in the sulfur-containing malodorous waste gas is 200 mg / m3, the mass concentration of volatile organic sulfide is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

[0070] The removal rates of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing malodorous waste gas of the comparative example are 91.1%, 73.5% and 77.6%, respectively.

[0071] The above description is only the preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed methods and technical contents to obtain equivalent embodiments with equivalent changes, without departing from the technical solution of the present application. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. Use of a metal-organic framework based bio-trickling filter media in the treatment of sulfur-containing malodorous waste gas, characterized in that: The metal organic framework-based bio-trickling filter filler comprises a soluble metal salt, an organic ligand and a binder; The method comprises the following steps: S21: loading a microbial flora on the surface of the metal organic framework-based bio-trickling filter filler to obtain a metal organic framework filler loaded with the microbial flora; S22: loading the metal organic framework filler loaded with the microbial flora into a bio-trickling tower; S23: spraying liquid on the top of the bio-trickling tower, the liquid flows through the metal organic framework filler loaded with the microbial flora and drops to the bottom of the bio-trickling tower; S24: introducing sulfur-containing foul gas into the bottom of the bio-trickling tower to make the sulfur-containing foul gas pass through the metal organic framework filler loaded with the microbial flora, and discharging the purified gas from the top of the tower; S25: collecting the liquid at the bottom of the bio-trickling tower, discharging the liquid, and recycling the liquid as the spraying water after biochemical treatment; The soluble metal salt comprises one or more combinations of lead nitrate, silver nitrate, barium nitrate, bismuth nitrate, calcium nitrate, chromium nitrate, copper nitrate, copper acetate, zinc nitrate and zinc acetate; The organic ligand comprises one or more combinations of trimesic acid, terephthalic acid, 3,5-pyridine dicarboxylic acid, 2,5-dimethyl terephthalic acid and 5-hydroxy terephthalic acid; The binder comprises one or more combinations of hydroxymethyl cellulose, chitosan, polyurethane and sodium alginate.

2. Use of the metal-organic framework-based biofiltration packing according to claim 1 for the treatment of sulfur-containing malodorous waste gases, characterized in that: In step S21, the preparation method of the metal organic framework filler loaded with the microbial flora comprises: S211: activating the metal organic framework-based bio-trickling filter filler with N-hydroxysuccinimide and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride; S212: dispersing the microorganism and the activated metal organic framework-based bio-trickling filter filler in PBS buffer to obtain the metal organic framework filler loaded with the microbial flora.

3. Use of the metal organic framework based bio-trickling filter packing according to claim 1 for the treatment of sulfur-containing malodorous waste gas, characterized in that: The spraying liquid is an aqueous solution containing inorganic nutrient salts, and is intermittently sprayed at a fixed time to maintain the bed moisture content at 65%-80%.

4. Use of the metal-organic framework-based biofiltration packing according to claim 1 in the treatment of sulfur-containing malodorous waste gas, characterized in that: The microbial flora is a composite microbial flora for purifying sulfur-containing foul gas, and the biological activity temperature of the microbial flora is 20-45℃.

5. Use of the metal-organic framework-based biofiltration packing according to claim 1 for the treatment of sulfur-containing malodorous waste gases, characterized in that: The preparation of the metal organic framework-based bio-trickling filter filler comprises the following steps: S11: mixing the soluble metal salt and the organic ligand in a solvent according to a molar ratio of 1:0.1-5, and heating to react to obtain a metal organic framework material; S12: mixing the metal organic framework material and the binder according to a mass ratio of 1:0.1-2 to granulate to obtain the metal organic framework-based bio-trickling filter filler.

6. Use of the metal-organic framework-based bio-trickling filter packing according to claim 5 for the treatment of sulfur-containing malodorous waste gases, characterized in that: The solvent comprises one or more combinations of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol and water.

7. Use of the metal-organic framework based bio-trickling filter packing according to claim 5 for the treatment of sulfur-containing malodorous waste gas, characterized in that: In step S11, the reaction temperature is 100-200℃, and the reaction time is 12-72 h.