Biological deodorant for garbage station and preparation method thereof

Abstract

The present invention discloses a biological deodorant for garbage stations and a preparation method thereof, which belongs to the field of biological deodorization technology. The biological deodorant is formed by mixing carefully screened Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum to form a composite microbial community, and the composite bacterial agent stock solution is obtained after cultivation. The preparation of the microbial carrier adopts natural materials such as kaolin, zeolite, and diatomaceous earth, combined with chemical synthetic materials such as polyether polyols and isocyanates, and is subjected to high-temperature roasting and alkaline solution treatment to form a carrier with high adsorption and stability. Finally, the sterilized microbial carrier is immersed in the composite bacterial agent stock solution to prepare an efficient and stable biological deodorant. Compared with the existing technology, the biological deodorant prepared by this method shows excellent deodorization effect and long-term stability in a simulated garbage station environment, providing a new solution for odor control in environments such as garbage stations.

Description

Technical Field

[0001] The present invention relates to the technical field of biological deodorization, in particular to a biological deodorant for garbage stations and a preparation method thereof. Background Art

[0002] With the rapid development of industrialization and urbanization, the amount of municipal solid waste generated is increasing. As key nodes for the collection and transfer of urban waste, garbage stations pose a particularly prominent environmental challenge. The foul odors generated by these stations not only impact the quality of life of surrounding residents but also pose a potential threat to human health. Therefore, the development of efficient and environmentally friendly bio-deodorizers for garbage stations is of great practical significance.

[0003] Traditional deodorization methods rely primarily on physical adsorption or chemical masking, such as activated carbon adsorption and ozone oxidation. However, these methods often suffer from issues such as short-term deodorization and the potential for secondary pollution. As an emerging environmentally friendly technology, biological deodorization utilizes the metabolic activity of microorganisms to convert malodorous substances into harmless substances. With its advantages of high treatment efficiency, zero secondary pollution, and low operating costs, it has become a hot topic in research and application.

[0004] In the field of bio-deodorization technology, the selection of microbial carriers is crucial. Ideal microbial carriers should possess good biocompatibility, a high specific surface area, a suitable pore structure, and mechanical strength to ensure efficient microbial fixation and sustained activity. However, existing microbial carriers are mostly made of a single material, such as organic carriers like polyacrylamide and polyvinyl alcohol, or inorganic carriers like diatomaceous earth and porous ceramics. These carriers have certain limitations in terms of chemical stability, mechanical strength, and biocompatibility.

[0005] Furthermore, the preparation of microbial agents is a key factor influencing the effectiveness of biological deodorization. Ideal microbial agents should possess robust malodor degradation capabilities, good environmental adaptability, and high activity stability. Although a variety of microbial agents have been developed for odor control, these agents often suffer from rapid activity loss and poor stability in practical applications, limiting their long-term application in harsh environments such as landfill sites.

[0006] The bio-deodorant of this invention utilizes a combination of natural mineral materials and chemically synthesized materials, enhancing not only the immobilization of microorganisms and the mechanical properties of the carrier, but also the chemical stability and biocompatibility of the carrier through a special post-processing process. Furthermore, by screening and optimizing the composite microbial community, the invention enhances the degradative capacity and environmental adaptability of the agent, providing a new solution for odor control in environments such as garbage stations.

[0007] Chinese invention patent CN110201204A discloses a biological deodorant carrier and its preparation method, as well as a biological deodorant and its preparation method, belonging to the field of biological deodorization technology. The biological deodorant carrier provided in this invention is prepared from the following raw materials in parts by weight: 9.5-10.0 parts clay, 4.0-4.5 parts attapulgite powder, 2.5-3.0 parts calcium carbonate, and 1.8-2.5 parts silicon dioxide. The biological deodorant carrier provided in this invention has excellent chemical stability, with a loss rate of less than 6% in strong acid, strong base, strong oxidant, and alcohol solutions. It also has a certain deodorizing function and exhibits even better deodorizing performance when used in combination with a biological deodorizing agent. However, its deodorizing effect and long-term stability still need to be improved. Summary of the Invention

[0008] In view of the limitations of the existing technology, the present invention aims to provide a biological deodorant for garbage stations and a preparation method thereof. Through innovative microbial carrier design and optimized preparation of microbial agents, it can achieve efficient and long-lasting deodorization effects and has good environmental adaptability and stability.

[0009] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0010] A preparation method of a biological deodorant for garbage stations is as follows, in parts by weight:

[0011] Step 1: Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum are mixed to form a composite microbial community; the composite microbial community is introduced into a tryptic soy bean liquid medium (TSB) for cultivation to promote its growth and reproduction, and after the cultivation process is completed, a composite bacterial agent stock solution is obtained;

[0012] Step 2: sterilize the microbial carrier with dry heat, immerse the sterilized microbial carrier in the composite bacterial agent stock solution obtained in step 1, take it out and drain it in the air until there are no water droplets on the surface, and obtain a biological deodorant for garbage stations.

[0013] The brewer's yeast, Bacillus amyloliquefaciens, Enterococcus faecalis and Lactobacillus plantarum are mixed in a mass ratio of 2-4:0.5-2:0.5-2:1-3.

[0014] The composite microbial community is introduced into trypticase soytone liquid culture medium TSB and cultured in a constant temperature box at 30-35° C. for 48-96 hours.

[0015] The microbial carrier is dry-heat sterilized at 100-150° C. for 1-5 hours.

[0016] The mass ratio of the microbial carrier to the composite bacterial agent stock solution obtained in step 1 is 0.5-2:2-4.

[0017] The microbial carrier is immersed in the composite bacterial agent stock solution obtained in step 1 for 5 to 24 hours.

[0018] The preparation method of the microbial carrier is as follows, in parts by weight:

[0019] S1. Weigh 0.5-1 parts of kaolin, 0.2-0.4 parts of zeolite, and 0.05-0.2 parts of diatomaceous earth, mix these raw materials with 2-4 parts of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.2-0.5 cm. Subsequently, place the wet spherical particles in an environment of 15-25° C. for 5-24 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage to form a pretreated support;

[0020] S2, weighing 60-80 parts of polyether polyol, 10-20 parts of poly(1,4-butylene adipate), 5-10 parts of water, 1-3 parts of polydimethylsiloxane, 0.05-0.2 parts of stannous octoate, 0.4-0.6 parts of 2-hydroxyethyltriethylenediamine, and 30-50 parts of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 35-50° C. to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing stirring to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0021] S3. Weigh 100-150 parts of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.05-0.2 parts of benzoyl peroxide, and mix the two raw materials in a reaction kettle to ensure that the initiator is evenly dispersed to form a treating agent;

[0022] S4. The post-treated product obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 10 to 20 hours. After the foaming is completed, the material is soaked in alkaline solution and then washed with water 1 to 3 times to obtain a microbial carrier.

[0023] In the high-temperature calcination stage, the calcination temperature is controlled at 700-900° C. and the duration is 2-4 hours.

[0024] The alkali solution soaking method comprises immersing the material in alkali solution, wherein the mass ratio of the material to the alkali solution is 0.5-2:8-12, and the soaking treatment is performed for 12-48 hours. The composition of the alkali solution is: a mixed solution of 8-12 mol / L sodium hydroxide aqueous solution and ethylene glycol in a volume ratio of 3-5:2-4.

[0025] In the present invention, the functions of each substance are as follows:

[0026] Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum: These microorganisms are mixed in specific mass ratios to form a complex microbial community, which grow and multiply in trypticase soy broth (TSB) and produce various enzymes and metabolites that can decompose odor-producing compounds.

[0027] Trypticase Soy Broth (TSB) provides nutrients and an environment for the growth and reproduction of complex microbial communities.

[0028] Natural mineral materials such as kaolin, zeolite, and diatomaceous earth are mixed to form the basic structure of the carrier, which is then calcined at high temperature to form a pretreated carrier with good adsorption and structural stability, providing attachment points for microorganisms.

[0029] Chemical synthetic materials such as polyether polyol, poly(1,4-butylene adipate) and polydimethylsiloxane are mixed with the pre-treated carrier in a reactor to form a post-treated product, which provides a protective and nutritional environment for microorganisms and enhances the mechanical properties of the carrier.

[0030] The polyether polyol is a polymer with an ether bond (-ROR-) in its backbone and two or more hydroxyl groups (-OH) at the end or side groups. It is typically produced by a ring-opening polymerization reaction between a low-molecular-weight polyol, polyamine, or active hydrogen-containing compound as an initiator and an olefin oxide (such as propylene oxide or ethylene oxide) in the presence of a catalyst. In the present invention, the polyether polyol serves as one of the primary raw materials for polyurethane foam formation. It reacts with isocyanate to produce a foam with a high specific surface area and excellent pore structure, providing a protective growth environment for microorganisms and enhancing the mechanical strength and chemical stability of the microbial carrier, thereby improving the deodorization efficiency and long-term stability of the biodeodorant.

[0031] Stannous octoate and 2-hydroxyethyltriethylenediamine act as catalysts to promote the chemical reaction between polyether polyol and isocyanate to form a stable polyurethane foam structure.

[0032] 1,2,3-Trivinylbenzene, as an active monomer, participates in the formation of the cross-linked network of polyurethane foam, enhancing the stability and mechanical strength of the foam.

[0033] 4,4'-benzylidene di(6-methyl-m-phenylene) tetraisocyanate, as an isocyanate raw material, reacts with polyether polyol and other components to form polyurethane foam. Its multiple isocyanate groups help form a highly cross-linked network structure.

[0034] Benzoyl peroxide acts as a free radical initiator, initiating polymerization and promoting foam formation.

[0035] In the alkali solution soaking treatment, sodium hydroxide and ethylene glycol are used to further solidify the polyurethane foam, and ethylene glycol is used as a solvent to help adjust the viscosity and reactivity of the alkali solution. This step helps to improve the surface properties and bioaffinity of the carrier.

[0036] The final microbial carrier combines the advantages of natural mineral materials and chemical synthetic materials, providing a suitable growth environment for microorganisms while ensuring the mechanical strength and chemical stability of the carrier, enabling it to play an effective role in environments such as garbage stations.

[0037] Compared with the existing technology, it has the following beneficial effects:

[0038] 1) By selecting and combining specific microbial communities, such as Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum, this invention achieves more efficient degradation of specific odorous substances in landfill environments. The synergistic effect of these microorganisms increases the degradation rate of odorous gases such as ammonia and hydrogen sulfide, significantly improving deodorization efficiency.

[0039] 2) By immobilizing microorganisms on specially treated carriers, such as kaolin, zeolite, and diatomaceous earth that have been calcined and treated with alkali, as well as specialized polyurethane foam, the biodeodorant exhibits improved long-term stability under simulated accelerated aging conditions. This stability ensures the deodorant's long-lasting effectiveness during storage and use, reducing the need for frequent replacement and lowering maintenance costs.

[0040] 3) This invention utilizes a method for preparing a microbial carrier that combines natural mineral materials with chemically synthesized materials. This method not only improves microbial attachment and protection but also optimizes the physical and chemical properties of the microbial carrier through precise control of the foaming and post-processing processes. This optimized preparation process improves deodorant production efficiency and quality control, making the product more suitable for practical applications. DETAILED DESCRIPTION

[0041] Main sources of substances:

[0042] Saccharomyces cerevisiae, a commercially available product, is from the China General Microorganism Culture Collection Center, with the scientific name Saccharomyces cerevisiae and the number CGMCC2.3973.

[0043] Bacillus amyloliquefaciens is a commercially available product from the China General Microorganism Culture Collection Center, with the scientific name Bacillus amyloliquefaciens and the number CGMCC1.857.

[0044] Enterococcus faecalis, a commercially available product, is from the China General Microbiological Culture Collection Center, with the scientific name Enterococcus faecalis and the number CGMCC1.15424.

[0045] Lactobacillus plantarum, a commercially available product, is from the China Agricultural Microbiological Culture Collection Center, with the scientific name Lactobacillus plantarum and the strain number ACCC 11118.

[0046] Trypticase soy broth TSB, catalog number: HB4114-19, purchased from Qingdao Hi-Tech Industrial Park Haibo Biotechnology Co., Ltd.

[0047] Kaolin, particle size: 800 mesh.

[0048] Zeolite, particle size: 200 mesh, silica content: 70-73 (%).

[0049] Diatomaceous earth, particle size: 100-200 mesh, SiO2 content ≥95 (%), Fe2O3 content ≤1.2 (%).

[0050] Polyether polyol, using polyether polyol EP330N, brand: Bluestar Dongda.

[0051] Polybutylene adipate, CAS: 150923-12-9, Mw: 1000, Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0052] Polydimethylsiloxane, product number: U31101115, Shandong Yousuo Chemical Technology Co., Ltd.

[0053] 4,4'-Benzalkonium bis(6-methyl-m-phenylene)tetraisocyanate, CAS number: 28886-07-9.

[0054] 2,2-Bis(4-isocyanatophenyl)hexafluoropropane, CAS number: 10224-18-7.

[0055] 4,4',4"-Triphenylmethane triisocyanate, CAS No.: 2422-91-5. The remaining raw materials in the examples and comparative examples of the present invention are all commercially available products.

[0056] The design idea of ​​the present invention is to prepare an efficient and stable biological deodorant for odor control in environments such as garbage stations. By carefully selecting and mixing a variety of beneficial microorganisms, a composite microbial community is formed. These microorganisms work together under specific fermentation conditions to enhance the deodorization effect. At the same time, the invention adopts a special microbial carrier preparation method, which combines high-temperature roasted natural mineral materials and high-performance polyurethane foam to provide microorganisms with a suitable growth environment and protection, thereby improving the adhesion, durability and biological activity of the deodorant. In addition, by optimizing the composition of the fermentation substance and the treatment process of the microbial carrier, the performance of the deodorant is further improved, so that it has better degradation efficiency and long-term stability in practical applications. This strategy of comprehensively considering microbial activity and carrier performance provides an innovative solution for the development of new environmentally friendly deodorization technologies.

[0057] Example 1

[0058] A method for preparing a biological deodorant for a garbage station is as follows:

[0059] Step 1: Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum are mixed in a mass ratio of 3:1:1:2 to form a composite microbial community; the composite microbial community is introduced into a tryptic soy beta-soybean liquid medium (TSB) and cultured in a 32° C. incubator for 72 hours to promote its growth and reproduction. After the culture process is completed, a composite bacterial agent stock solution is obtained;

[0060] Step 2: dry-heat sterilize the microbial carrier at 120° C. for 3 hours, immerse the sterilized microbial carrier in the composite bacterial agent stock solution obtained in step 1 for 12 hours, and the mass ratio of the microbial carrier to the composite bacterial agent stock solution obtained in step 1 is 1:3. Take it out and drain it in the air until there are no water droplets on the surface to obtain a biological deodorant for garbage stations.

[0061] The preparation method of the microbial carrier is as follows:

[0062] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0063] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0064] S3. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0065] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0066] Example 2

[0067] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0068] The preparation method of the microbial carrier is as follows:

[0069] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0070] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of α-methylstyrene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0071] S3. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0072] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0073] Example 3

[0074] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0075] The preparation method of the microbial carrier is as follows:

[0076] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0077] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of m-fluorostyrene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0078] S3. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0079] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0080] Example 4

[0081] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0082] The preparation method of the microbial carrier is as follows:

[0083] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0084] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0085] S3. Weigh 120 kg of 2,2-bis(4-isocyanatophenyl)hexafluoropropane and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0086] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0087] Example 5

[0088] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0089] The preparation method of the microbial carrier is as follows:

[0090] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0091] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0092] S3. Weigh 120 kg of 4,4',4"-triphenylmethane triisocyanate and 0.1 kg of benzoyl peroxide, mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0093] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0094] Comparative Example 1

[0095] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0096] The preparation method of the microbial carrier is as follows:

[0097] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0098] S2, weighing 70kg polyether polyol EP330N, 15kg poly(1,4-butylene adipate), 7kg water, 2kg polydimethylsiloxane, 0.1kg stannous octoate, 0.5kg 2-hydroxyethyltriethylenediamine, and 40kg divinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-processed product;

[0099] S3. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0100] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0101] Comparative Example 2

[0102] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0103] The preparation method of the microbial carrier is as follows:

[0104] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0105] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of styrene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0106] S3. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0107] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0108] Comparative Example 3

[0109] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0110] The preparation method of the microbial carrier is as follows:

[0111] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage with a calcination temperature controlled at 800° C. for 3 hours to form a pretreated support;

[0112] S2, weighing 70kg of polyether polyol EP330N, 15kg of poly(1,4-butylene adipate), 7kg of water, 2kg of polydimethylsiloxane, 0.1kg of stannous octoate, 0.5kg of 2-hydroxyethyltriethylenediamine, and 40kg of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 40°C to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing to stir to ensure that it is evenly dispersed in the mixture to form a post-treated product;

[0113] S3, weighing 120kg of diphenylmethane diisocyanate and 0.1kg of benzoyl peroxide, and mixing the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0114] S4. The post-treated material obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0115] Comparative Example 4

[0116] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0117] The preparation method of the microbial carrier is as follows:

[0118] S1. Weigh 0.8 kg of kaolin, 0.3 kg of zeolite, and 0.1 kg of diatomaceous earth, mix these raw materials with 3 kg of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.3 cm. Subsequently, the wet spherical particles are placed in an environment of 20° C. and aged for 12 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature roasting stage, the roasting temperature is controlled at 800° C., and the duration is 3 hours to obtain a microbial carrier;

[0119] Comparative Example 5

[0120] The preparation method of a biological deodorant for garbage stations is basically the same as that in Example 1, the only difference being the preparation method of the microbial carrier.

[0121] The preparation method of the microbial carrier is as follows:

[0122] S1. Weigh 70 kg of polyether polyol EP330N, 15 kg of poly(1,4-butylene adipate), 7 kg of water, 2 kg of polydimethylsiloxane, 0.1 kg of stannous octoate, 0.5 kg of 2-hydroxyethyltriethylenediamine, and 40 kg of 1,2,3-trivinylbenzene. Thoroughly mix these raw materials in a reactor. Maintain the temperature in the reactor at 40° C. to promote interaction between the raw materials until a uniform mixture is formed. Continue stirring to form a post-processed product.

[0123] S2. Weigh 120 kg of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.1 kg of benzoyl peroxide, and mix the two raw materials in a reactor to ensure that the initiator is evenly dispersed to form a treating agent;

[0124] S3. The post-treated material obtained in step S1 and the treatment agent prepared in step S2 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 15 hours. After the foaming is completed, the material is soaked in alkali solution. The alkali solution soaking method is to immerse the material in alkali solution, the mass ratio of the material to the alkali solution is 1:10, and the soaking treatment is for 24 hours. The alkali solution composition is: 10 mol / L sodium hydroxide aqueous solution and ethylene glycol are prepared into a mixed solution in a volume ratio of 4:3; then washed with distilled water 3 times, and the amount of distilled water used each time is 3 times the weight of the material to obtain a microbial carrier.

[0125] Test Example 1

[0126] Deodorization effect test

[0127] The biological deodorants obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were uniformly mixed with tap water in a mass ratio of 1:1, and brown sugar in an amount of 1 / 2 the mass of the biological deodorant was added, and the mixture was stirred at 200 r / min for 2 h to obtain a preparation. The preparation was sprayed on kitchen waste using a spray bottle in a sealed indoor environment. 2 g of the preparation containing the microbial deodorant was added to each kilogram of kitchen waste. After 1 hour, the NH3 and H2S gas content indicators were tested using an HF-900 gas chromatograph, and the degradation rate was calculated. The degradation rate (%) = [(odor gas concentration before deodorization - odor gas concentration after deodorization treatment) / odor gas concentration before deodorization] × 100%. The hydrogen sulfide concentration before treatment was 60 ppm, and the ammonia concentration was 75 ppm.

[0128] The test results are shown in Table 1.

[0129] Table 1

[0130]

[0131] Test Example 2

[0132] The long-term stability of the biodeodorants was evaluated. Specifically, samples of the biodeodorants prepared in Examples 1-5 and Comparative Examples 1-5 were stored at 30°C for 40 days to simulate the accelerated aging of the microbial strains. Subsequently, 1 gram of the biodeodorant was removed from each sample and placed in a 250-ml Erlenmeyer flask containing sterile glass beads and 100 ml of PBS buffer. These flasks were placed on a thermostatic magnetic stirrer and stirred for 2 hours to ensure uniform dispersion of the biodeodorant. After stirring, the samples were subjected to a series of serial dilutions and further diluted with sterile water. The diluted samples were evenly spread on specific culture media, including Lactobacillus, Bacillus, and Saccharomyces cerevisiae, to promote the growth of the corresponding microorganisms. These cultures were then incubated at 37°C for 28 hours. After the incubation period, the number of colonies on the culture media was counted to assess the survival of each active strain in the composite microbial inoculum after 40 days of storage at 30°C.

[0133] The test results are shown in Table 2.

[0134] Table 2

[0135]

[0136] It can be seen from the data in Tables 1 and 2 that the biological deodorant for garbage stations prepared in Example 1 has the best deodorizing effect and long-term stability.

[0137] In Example 1 of the present invention, 1,2,3-trivinylbenzene is used as an olefin monomer, which has three vinyl functional groups, which enables it to provide more cross-linking points in the polymerization reaction, thereby enhancing the mechanical strength and structural stability of the final microbial carrier. In addition, the high reactivity of 1,2,3-trivinylbenzene helps to increase the cross-linking density of the polymer, which is beneficial for improving the porosity and adsorption properties of the microbial carrier. These characteristics make the microbial carrier prepared with 1,2,3-trivinylbenzene as raw material perform better in terms of deodorization effect and long-term stability. In contrast, although other olefin monomers such as α-methylstyrene, m-fluorostyrene, divinylbenzene and styrene can also participate in the polymerization reaction, due to their small number of vinyl functional groups, they are not as effective as 1,2,3-trivinylbenzene in forming a highly cross-linked polymer network.

[0138] In Example 1 of the present invention, 4,4'-benzylidene bis(6-methyl-m-phenylene) tetraisocyanate was used as the isocyanate raw material. Its molecule contains four isocyanate groups (-NCO), which enables it to form more crosslinking points during the polymerization reaction, thereby enhancing the polymer's network structure and overall stability. In contrast, while 2,2-bis(4-isocyanatophenyl)hexafluoropropane in Example 4 and 4,4',4"-triphenylmethane triisocyanate in Example 5 also exhibit good polymerization properties, their smaller number of functional groups results in a relatively low crosslinking density, which in turn affects the mechanical strength and durability of the final product. The diphenylmethane diisocyanate used in Comparative Example 3 also presents similar issues. Therefore, the high functionality and strong crosslinking ability of 4,4'-benzylidene bis(6-methyl-m-phenylene) tetraisocyanate make the biological deodorant of Example 1 superior in terms of deodorization effectiveness and long-term stability.

[0139] In Example 1 of the present invention, by adopting a complete microbial carrier, that is, combining natural mineral materials and chemical synthetic materials, the prepared biological deodorant for garbage stations exhibited excellent deodorization effect and long-term stability. The combination of natural mineral materials and chemical synthetic materials produced a significant synergistic effect, among which natural mineral materials such as kaolin, zeolite and diatomaceous earth provided stable attachment points and a suitable growth environment for microorganisms due to their unique pore structure and surface properties, thereby enhancing the immobilization effect of microorganisms. Chemical synthetic materials, such as polyether polyols and isocyanates, formed a carrier with a specific porosity and mechanical strength by precisely controlling the foaming and curing processes, which not only protected the microorganisms from environmental stress, but also improved the durability and biocompatibility of the carrier. This combination takes advantage of the eco-friendliness of natural materials and the designability of synthetic materials to achieve a more efficient and lasting deodorization effect, while ensuring the long-term stability and high efficiency of the biological deodorant. Furthermore, 1,2,3-trivinylbenzene, as an active monomer, exhibits terpolymeric properties that help form a more stable polymer network. This network likely undergoes a cross-linking reaction with the multiple isocyanate groups in 4,4'-benzylidene di(6-methyl-m-phenylene) tetraisocyanate, forming a highly cross-linked polyurethane foam structure. This structure not only enhances the mechanical strength of the carrier but also potentially improves its ability to immobilize microorganisms, providing better protection for them. This, in turn, maintains a high survival rate of active strains during simulated accelerated aging, thereby enhancing the long-term stability and effectiveness of the deodorant.

Claims

1. A method for preparing a biological deodorant for a garbage station, characterized in that: In parts by weight: Step 1: Saccharomyces cerevisiae, Bacillus amyloliquefaciens, Enterococcus faecalis, and Lactobacillus plantarum are mixed to form a composite microbial community; the composite microbial community is introduced into a tryptic soy bean liquid medium (TSB) for cultivation to promote its growth and reproduction, and after the cultivation process is completed, a composite bacterial agent stock solution is obtained; Step 2: sterilize the microbial carrier with dry heat, immerse the sterilized microbial carrier in the composite bacterial agent stock solution obtained in Step 1, take it out and drain it in the air until there are no water droplets on the surface, and obtain a biological deodorant for garbage stations; The preparation method of the microbial carrier is as follows, in parts by weight: S1. Weigh 0.5-1 parts of kaolin, 0.2-0.4 parts of zeolite, and 0.05-0.2 parts of diatomaceous earth, mix these raw materials with 2-4 parts of water to form a uniform slurry, and form the slurry into wet spherical particles with a particle size of 0.2-0.5 cm. Subsequently, place the wet spherical particles in an environment of 15-25° C. for 5-24 hours to promote uniform distribution of moisture. The aged particles enter a high-temperature calcination stage to form a pretreated support; S2, weighing 60-80 parts of polyether polyol, 10-20 parts of poly(1,4-butylene adipate), 5-10 parts of water, 1-3 parts of polydimethylsiloxane, 0.05-0.2 parts of stannous octoate, 0.4-0.6 parts of 2-hydroxyethyltriethylenediamine, and 30-50 parts of 1,2,3-trivinylbenzene, and thoroughly mixing these raw materials in a reactor, maintaining the temperature in the reactor at 35-50° C. to promote interaction between the raw materials until a uniform mixture is formed, adding the pretreated support prepared in step S1, and continuing stirring to ensure that it is evenly dispersed in the mixture to form a post-treated product; S3. Weigh 100-150 parts of 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate and 0.05-0.2 parts of benzoyl peroxide, and mix the two raw materials in a reaction kettle to ensure that the initiator is evenly dispersed to form a treating agent; S4. The post-treated product obtained in step S2 and the treatment agent prepared in step S3 are fully mixed in a reactor to ensure that the two are completely mixed. The mixed material is poured into a mold and subjected to a foaming reaction at room temperature for 10 to 20 hours. After the foaming is completed, the material is soaked in alkali solution and then washed with water 1 to 3 times to obtain a microbial carrier; The calcination temperature in the high temperature calcination stage is controlled at 700-900°C and the duration is 2-4 hours; The alkali solution soaking method comprises immersing the material in alkali solution, wherein the mass ratio of the material to the alkali solution is 0.5-2:8-12, and the soaking treatment is performed for 12-48 hours. The composition of the alkali solution is: a mixed solution of 8-12 mol / L sodium hydroxide aqueous solution and ethylene glycol in a volume ratio of 3-5:2-4.

2. The method for preparing a biological deodorant for garbage stations according to claim 1, wherein: The brewer's yeast, Bacillus amyloliquefaciens, Enterococcus faecalis and Lactobacillus plantarum are mixed in a mass ratio of 2-4:0.5-2:0.5-2:1-3.

3. The method for preparing a biological deodorant for garbage stations according to claim 1, wherein: The composite microbial community is introduced into trypticase soytone liquid culture medium TSB and cultured in a constant temperature box at 30-35° C. for 48-96 hours.

4. The method for preparing a biological deodorant for garbage stations according to claim 1, wherein: The microbial carrier is dry-heat sterilized at 100-150° C. for 1-5 hours.

5. The method for preparing a biological deodorant for garbage stations according to claim 1, wherein: The mass ratio of the microbial carrier to the composite bacterial agent stock solution obtained in step 1 is 0.5-2:2-4.

6. The method for preparing a biological deodorant for garbage stations according to claim 1, wherein: The microbial carrier is immersed in the composite bacterial agent stock solution obtained in step 1 for 5 to 24 hours.

7. A biological deodorant for garbage stations, characterized in that: Prepared by the preparation method according to any one of claims 1 to 6.

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