Bio-trickling filter filler based on metal organic framework, preparation method and application of bio-trickling filter filler

Abstract

The invention discloses a bio-trickling filter filler based on a metal organic framework. The bio-trickling filter filler comprises soluble metal salt, an organic ligand and an adhesive. The preparation method comprises the following steps: mixing a soluble metal salt and an organic ligand in a solvent, and carrying out a heating reaction to obtain the metal organic framework material, mixing and granulating the metal organic framework material and an adhesive to obtain the bio-trickling filter filler based on the metal organic framework. The bio-trickling filter filler is simple in preparation method, stable in structural performance, extremely large in specific surface area and high in biological adsorption capacity, has a good adsorption effect on sulfur-containing foul waste gas, is relatively high in degradation efficiency, can effectively combine an adsorption method and a biological method, and can play the advantages of the adsorption method and the biological method; the removal rate of hydrogen sulfide, organic sulfide and benzene series in the sulfur-containing foul waste gas can reach 99.5%.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental protection purification, and specifically relates to a bio-trickling filter filler based on a metal organic framework, a preparation method and an application thereof. Background Art

[0002] The sewage treatment plant of petrochemical enterprises is one of the main sources of odor pollution. A large amount of odorous waste gas is generated during the oil refining process, part of which is discharged into the atmosphere through leakage, bubbling and leaking. Most of the odorous substances are miscible with water and eventually enter the sewage treatment plant with sewage. The main components of these odor pollution sources are H2S, organic sulfides, ammonia, organic acids, benzene series, etc. As people pay more attention to the problem of odor pollution, various treatment methods have emerged, mainly including combustion method, oxidation method, absorption method, adsorption method, biological method, etc. Physical and chemical treatment methods have problems such as large investment, complex operation, high operating cost, and easy to produce secondary pollution. Biological deodorization has become the main deodorization method in recent years due to its low investment, low operating cost, reliable performance, easy management, good treatment effect, and low secondary pollution.

[0003] Biological treatment of malodorous waste gas is the most economical and effective method. The biological purification methods of malodorous waste gas include biological absorption tank, biological washing tank, biological trickling filter tower and biological filtration tank, which have good treatment effect and convenient operation. The main body of the biological trickling filter tower is a packed tower with one or more layers of fillers. The surface of the filler is a biofilm several millimeters thick formed by microorganisms. The liquid containing soluble inorganic domesticated nutrient solution is evenly sprayed on the filler from the top of the tower. The liquid flows from top to bottom, and then is discharged from the bottom of the tower and recycled. The malodorous waste gas enters the biological trickling filter tower from the bottom of the tower, and is purified by contact with the wetted biofilm during the rising process. The purified gas is discharged from the top of the tower.

[0004] People have developed a variety of filter fillers that can attach a variety of microorganisms, such as compost, slag, activated carbon, zeolite, peat, plastics and synthetic resins. The fillers can provide a variety of microbial communities to inhabit and grow, forming a stable ecological community. The surface of the filler is covered with biofilm, which increases the biomass, thereby improving the odor treatment efficiency and oxygen utilization. The filler is the core component of biological filtration, biological trickling filter and biological fluidized bed devices. It is both a support carrier for biological growth and a gas-liquid two-phase mass transfer medium. Its performance directly affects the deodorization effect.

[0005] Metal Organic Frameworks (MOFs) are a new type of porous material, composed of a variety of metal centers and a variety of organic ligands, with an adjustable structure. They are widely used in gas adsorption, separation, catalysis, energy, and radiation detection. MOFs are used in the field of organic waste gas treatment by adsorption. With their high specific surface area, good stability, and structural variability, they have certain application prospects in the field of organic waste gas adsorption. Dong Xiaojun et al. recorded the use of MOFs materials to treat acidic gases in the Journal of Shandong Jianzhu University, Vol. 38 (Issue 2), pages 87-91, with good results.

[0006] Adsorption method is a simple and direct method with obvious adsorption effect, which has attracted people's attention. However, its development is hindered by high cost, secondary pollution and low recycling rate. 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, which has attracted people's attention. If microorganisms are used directly 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 microorganisms. Therefore, the simple use of microorganisms is limited in actual practice.

[0007] In the patent application No. 202011388437.9, a spray liquid for waste gas and odor purification and its preparation method are described in which metal organic framework materials are added to the spray liquid, and the metal organic framework materials with high pore volume are used to absorb the pollution in the waste gas and odor to increase the capture rate of hydrophobic substances. This method only uses a photocatalytic metal organic framework to absorb pollution, and no microorganisms are added.

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

[0009] The object of the present invention is to provide a biotrickling filter filler based on a metal organic framework, a preparation method and an application thereof, so as to solve the problems raised in the above background technology.

[0010] To achieve the above object, the present invention provides the following technical solution: a metal organic framework-based biotrickling filter filler, comprising

[0011] Soluble metal salts, organic ligands and binders.

[0012] Preferably, the soluble metal salt includes 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.

[0013] In any of the above schemes, it is preferred that the organic ligand includes a combination of one or more of trimesic acid, terephthalic acid, 3,5-pyridinedicarboxylic acid, 2,5-dimethylterephthalic acid, and 5-hydroxyisophthalic acid.

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

[0015] A method for preparing a biotrickling filter filler based on a metal organic framework comprises the following steps:

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

[0017] S12: The metal organic framework material and the binder are mixed and granulated in a mass ratio of 1:0.1-2 to obtain a biotrickling filter filler based on the metal organic framework.

[0018] In any of the above schemes, it is preferred that 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 schemes, the adhesive comprises a combination of one or more of hydroxymethyl cellulose, chitosan, polyurethane and sodium alginate.

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

[0021] An application of a biotrickling filter filler based on a metal organic framework in the treatment of sulfur-containing malodorous waste gas comprises the following steps:

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

[0023] S22: loading the metal organic framework filler loaded with microbial flora into a biotrickling filter;

[0024] S23: performing a spraying operation on the top of the bio-trickling filter using a spray liquid, wherein the spray liquid flows through the metal organic framework filler loaded with microbial flora and drips to the bottom of the bio-trickling filter;

[0025] S24, introducing sulfur-containing odorous waste gas into the bottom of the biotrickling filter tower, so as to allow the sulfur-containing odorous waste gas to pass through the metal organic framework filler loaded with microbial flora, and the purified gas is discharged from the top of the tower;

[0026] S25: The spray liquid at the bottom of the biotrickling filter is collected and discharged, and then recycled as spray water after biochemical treatment.

[0027] In any of the above schemes, preferably, in step S21, the method for preparing the metal organic framework filler loaded with microbial flora comprises:

[0028] S211: Metal-organic framework-based biotrickling filter media activated with N-hydroxysuccinimide and N(3-dimethylaminopropyl)N'ethylcarbodiimide hydrochloride;

[0029] S212: The microorganisms and the activated metal-organic framework-based biotrickling filter filler are then dispersed together in a PBS buffer to obtain a metal-organic framework filler loaded with microbial flora.

[0030] Preferably in any of the above schemes, the biotrickling filter tower includes a tower body, a sprayer arranged at the upper part of the tower body, a metal organic framework filler arranged in the middle part of the tower body, a gas distributor arranged at the lower part of the tower body and an air inlet arranged at the bottom of the tower body, the bottom of the tower body is a spray liquid storage tank, and the spray liquid storage tank is provided with a drain port.

[0031] Preferably, in any of the above schemes, the spraying liquid is an aqueous solution containing inorganic nutrient salts, and the spraying is performed intermittently and regularly to maintain the moisture content of the bed at 65%-80%.

[0032] In any of the above schemes, it is preferred that 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°C.

[0033] The sulfur-containing malodorous waste gas mainly refers to the malodorous waste gas discharged from the sewage treatment facilities of petrochemical enterprises, which has the characteristics of low concentration and large amount. The mass concentration of hydrogen sulfide is 10-200 mg / m3, the mass concentration of volatile organic sulfides (C1-C3 mercaptans and sulfides, 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 invention are as follows: Based on metal organic framework materials (MOF), the present invention synthesizes MOF materials with excellent performance by selecting metal centers and organic ligands, and uses granulation to make them into bio-trickling filter fillers, and loads microbial flora so that they are suitable for the treatment process of sulfur-containing odorous waste gas;

[0035] The preparation method of the bio-trickling filter filler is simple, the structure and performance are stable, it has a large specific surface area and a strong biological adsorption capacity, and at the same time it has a good adsorption effect on sulfur-containing malodorous waste gas, and a high degradation efficiency. It can effectively combine the adsorption method and the biological method and give play to the advantages of both. Compared with the prior art, the removal rate of hydrogen sulfide, organic sulfide, and benzene series in sulfur-containing malodorous waste gas can reach 99.5%. DETAILED DESCRIPTION

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

[0037] Embodiment 1:

[0038] (1) The present embodiment provides a method for preparing a biotrickling filter filler based on a metal organic framework, comprising the following steps: dissolving 0.15 mol of barium nitrate and 0.1 mmol of 3,5-pyridinedicarboxylic acid in 100 ml of deionized water and N,N-dimethylformamide, stirring to obtain a suspension, heating the suspension at 150° C. in a drying oven for 24 h to obtain a metal organic framework material (MOF), then granulating the MOF and a binder (hydroxymethyl cellulose) in a certain mass ratio (MOF: binder = 2:1), adding 150 mL of water for mixing and shaping, granulating the obtained mixture and freeze-drying it to obtain a biotrickling filter filler based on a metal organic framework.

[0039] (2) The preparation process of the metal organic framework filler loaded with microbial flora comprises the following steps: dispersing 0.1 mol N-hydroxysuccinimide (NHS), 0.1 mol N(3-dimethylaminopropyl)N'ethylcarbodiimide hydrochloride (EDC) and 5 g of dried metal organic framework filler in 500 mL of citrate buffer solution at pH 6.0, stirring at room temperature for 24 h for activation, expanding and culturing the domesticated composite microbial flora specially used for odorous waste gas purification in a liquid culture medium and then centrifuging, dispersing the bacteria and the activated metal organic framework filler together in PBS buffer, placing them on a constant temperature shaker for 24 h at 35°C and 250 rpm, and firmly loading the bacteria on the surface of the material through chemical bonds between a large number of carboxyl functional groups on the upper surface and the amino groups on the bacterial surface.

[0040] (3) The prepared metal organic framework filler loaded with microbial flora is loaded into a biotrickling filter to conduct 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 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 in this embodiment are 100%, 100%, 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0042] Embodiment 2:

[0043] (1) This embodiment provides a method for preparing a biotrickling filter filler based on a metal organic framework, comprising the following steps: dissolving 0.1 mol of barium nitrate and 0.1 mmol of terephthalic acid in 100 ml of deionized water, stirring to obtain a suspension, heating the suspension at 150° C. in a drying oven for 36 h to obtain a metal organic framework material (MOF), then granulating the MOF and a binder (polyurethane) in a certain mass ratio (MOF: binder = 3:1), adding 150 mL of water for mixing and shaping, granulating the obtained mixture and freeze-drying it to obtain a biotrickling filter filler based on a 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 is loaded into a biotrickling filter to carry out 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 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 in this embodiment are 100%, 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0047] Embodiment 3:

[0048] (1) This embodiment provides a method for preparing a bio-trickling filter filler based on a metal organic framework, comprising the following steps: dissolving 0.1 mol of chromium nitrate and 0.1 mmol of trimesic acid in 100 ml of N,N-dimethylacetamide, stirring to obtain a suspension, heating the suspension at 180° C. in a drying oven for 36 h to obtain a metal organic framework material (MOF). Subsequently, MOF and a binder (sodium alginate) are granulated in a certain mass ratio (MOF: binder = 1:1), and 150 mL of water is added for mixing and shaping, and the obtained mixture is granulated and freeze-dried to obtain a bio-trickling filter filler based on a metal organic framework.

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

[0050] (3) The prepared metal organic framework filler loaded with microbial flora is loaded into a biotrickling filter to conduct 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 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 in this embodiment are 100%, 99.9%, 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0052] Embodiment 4:

[0053] (1) This embodiment provides a method for preparing a bio-trickling filter filler based on a metal organic framework, comprising the following steps: dissolving 0.2 mol of copper acetate and 0.1 mmol of 5-hydroxyisophthalic acid in 100 ml of deionized water and N,N-dimethylacetamide, stirring to obtain a suspension, heating the suspension at 120° C. in a drying oven for 48 h to obtain a metal organic framework material (MOF). Subsequently, MOF and a binder (chitosan) are granulated in a certain mass ratio (MOF: binder = 1:1), and 150 mL of water is added for mixing and shaping, and the obtained mixture is granulated and freeze-dried to obtain a bio-trickling filter filler based on a metal organic framework.

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

[0055] (3) The prepared metal organic framework filler loaded with microbial flora is loaded into a biotrickling filter to conduct 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 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 in this embodiment are 99.9%, 99.8%, and 99.8%, 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0057] Embodiment 5:

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

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

[0060] (3) The prepared metal organic framework filler loaded with microbial flora is loaded into a biotrickling filter to conduct 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 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 in this embodiment are 99.8%, 99.7%, and 99.8%, 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0062] Embodiment 6:

[0063] (1) The present embodiment provides a method for preparing a biotrickling filter filler based on a metal organic framework, 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 at 150° C. in a drying oven for 18 h to obtain a metal organic framework material (MOF), then granulating the MOF and a binder (hydroxymethyl cellulose) in a certain mass ratio (MOF: binder = 2:1), adding 150 mL of water for mixing and shaping, granulating the obtained mixture and freeze-drying it to obtain a biotrickling filter filler based on a metal organic framework.

[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 loaded into a biotrickling filter to carry out 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 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 in this 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 sulfides is 500 mg / m3, and the mass concentration of benzene series is 2000 mg / m3.

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

[0067] Comparative Example 1:

[0068] Traditional filler: The traditional filler of the biotrickling filter is expanded clay with a particle size of 3-6 mm.

[0069] An experiment was conducted on the treatment 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 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 in this 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 sulfides 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 in this comparative example are 91.1%, 73.5% and 77.6% respectively.

[0071] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes by using the methods and technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A biotrickling filter filler based on a metal organic framework, characterized in that: include Soluble metal salts, organic ligands and binders.

2. The metal organic framework-based biotrickling filter filler according to claim 1, characterized in that: The soluble metal salt includes one or more of lead nitrate, silver nitrate, barium nitrate, bismuth nitrate, calcium nitrate, chromium nitrate, copper nitrate, copper acetate, zinc nitrate and zinc acetate.

3. The metal organic framework-based biotrickling filter filler according to claim 1, characterized in that: The organic ligand includes a combination of one or more of trimesic acid, terephthalic acid, 3,5-pyridinedicarboxylic acid, 2,5-dimethylterephthalic acid, and 5-hydroxyisophthalic acid.

4. The metal organic framework-based biotrickling filter filler according to claim 1, characterized in that: The adhesive comprises one or more combinations of hydroxymethyl cellulose, chitosan, polyurethane and sodium alginate.

5. A method for preparing a biotrickling filter filler based on a metal organic framework according to any one of claims 1 to 4, characterized in that: The following steps are involved: S11: mixing a soluble metal salt and an organic ligand in a solvent at a molar ratio of 1:0.1-5, heating and reacting to obtain a metal organic framework material; S12: The metal organic framework material and the binder are mixed and granulated in a mass ratio of 1:0.1-2 to obtain a biotrickling filter filler based on the metal organic framework.

6. The method for preparing a biotrickling filter filler based on a metal organic framework according to claim 5, characterized in that: The solvent includes a combination of one or more of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol and water.

7. The method for preparing a biotrickling filter filler based on a metal organic framework according to claim 5, characterized in that: The adhesive comprises one or more combinations of hydroxymethyl cellulose, chitosan, polyurethane and sodium alginate.

8. The method for preparing a biotrickling filter filler based on a metal organic framework according to claim 5, characterized in that: In step S1, the reaction temperature is 100-200°C, and the reaction time is 12-72h.

9. An application of a metal organic framework-based biotrickling filter filler according to any one of claims 1-4, 6-8 in the treatment of sulfur-containing malodorous waste gas, characterized in that: The following steps are involved: S21: loading the microbial flora onto the surface of the metal organic framework-based biotrickling filter filler to obtain the metal organic framework filler loaded with the microbial flora; S22: loading the metal organic framework filler loaded with microbial flora into a biotrickling filter; S23: performing a spraying operation on the top of the bio-trickling filter using a spray liquid, wherein the spray liquid flows through the metal organic framework filler loaded with microbial flora and drips to the bottom of the bio-trickling filter; S24, introducing sulfur-containing odorous waste gas into the bottom of the biotrickling filter tower, so as to allow the sulfur-containing odorous waste gas to pass through the metal organic framework filler loaded with microbial flora, and the purified gas is discharged from the top of the tower; S25: The spray liquid at the bottom of the biotrickling filter is collected and discharged, and then recycled as spray water after biochemical treatment.

10. An application of the metal organic framework-based biotrickling filter filler according to claim 9 in the treatment of sulfur-containing odorous waste gas, characterized in that: In step S21, the method for preparing the metal organic framework filler loaded with microbial flora comprises: S211: Metal-organic framework-based biotrickling filter media activated with N-hydroxysuccinimide and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride; S212: The microorganisms and the activated metal-organic framework-based biotrickling filter filler are then dispersed together in a PBS buffer to obtain a metal-organic framework filler loaded with microbial flora.

11. An application of the metal organic framework-based biotrickling filter filler according to claim 9 in the treatment of sulfur-containing malodorous waste gas, characterized in that: The spraying liquid is an aqueous solution containing inorganic nutrient salts, and is sprayed intermittently and regularly to maintain the moisture content of the bed at 65%-80%.

12. An application of the metal organic framework-based biotrickling filter filler according to claim 9 in the treatment of sulfur-containing malodorous waste gas, characterized in that: The microbial flora is a composite microbial flora used for purifying sulfur-containing malodorous waste gas, and the biological activity temperature of the microbial flora is 20-45°C.