Deodorizing and odor-removing composite microbial preparation and preparation method thereof

Abstract

The application discloses a kind of deodorization and odor-removing composite microbial preparation and preparation method thereof, belong to microbial preparation technical field, the composite microbial preparation includes the following components: 10-20 weight parts modified adsorption carrier and 40-50 weight parts composite microbial liquid. Among them, the modified adsorption carrier is made by hybrid skeleton material after secondary impregnation of metal salt, calcination and coating polydopamine, and the composite microorganism is at least two kinds of plant-like lactobacillus, rhamnose lactobacillus and cheese-like lactobacillus. The composite microbial preparation prepared by the application has remarkable deodorization and odor-removing effect, high stability, simple process, and has wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of microbial preparation technology, specifically relating to a deodorizing and odor-removing compound microbial preparation and its preparation method. Background Technology

[0002] Odor pollution is widespread in household waste, industrial emissions, and municipal facilities. Its main components include hydrogen sulfide, ammonia, and volatile organic compounds, which not only harm human health but also exacerbate environmental pollution. Traditional deodorization technologies, such as chemical oxidation and physical adsorption, can mask odors in the short term, but they suffer from drawbacks such as chemical residues, secondary pollution, and high costs. For example, chemical deodorants may cause skin irritation and require frequent use, while physical adsorption materials need to be replaced regularly and cannot decompose odorous substances. In contrast, biological deodorization technology converts odorous substances into harmless carbon dioxide and water through microbial metabolism, offering advantages such as environmental friendliness and long-lasting effectiveness. However, existing microbial preparations still face challenges such as limited strains, complex production processes, and insufficient adaptability.

[0003] For example, Chinese patent CN1411872A discloses a microbial deodorant and its preparation method, which uses prions and small elliptic yeasts as strains, and obtains a mixed fermentation broth through seed culture and fermentation culture, and then adds an appropriate amount of fragrance. It solves the problem of odor from domestic waste and feces by inhibiting the physiological activity of odor-causing microorganisms and using odor-causing substances as its own nutrients. However, the strains of this microbial deodorant are relatively limited, including only yeast, and its adaptability is insufficient. Chinese patent CN104667320A discloses a composite microbial deodorizer for treating municipal solid waste and its preparation method. The raw materials include composite photosynthetic bacteria powder, Bacillus subtilis powder, composite Aspergillus powder, and composite yeast powder. Through the synergistic effect of various beneficial bacteria—including *Thiobacillus rubrum* (degrading hydrogen sulfide), *Rhodospirillum rubrum* (degrading fatty acid odors and ammonia), *Aspergillus oryzae* (rich in proteases and cellulases), *Bacillus subtilis* (degrading ammonia), *Rhizopus oryzae* (rich in lactic acid), *Saccharomyces cerevisiae* (producing ethanol), and *Candida guinea* (rich in aroma-producing substances)—this effectively improves the ecological environment of municipal solid waste and reduces odor emissions. However, the process of this composite microbial deodorizer requires multiple fermentation steps and complex post-treatment, resulting in a long production cycle and low equipment utilization, limiting large-scale application. Therefore, there is an urgent need to develop a novel deodorizing composite microbial preparation and its preparation method, which has advantages such as significant deodorizing effect, strong environmental adaptability, high application stability, and simple preparation process. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention provides a deodorizing and odor-removing compound microbial preparation, which adds a specific modified adsorption carrier to the compound microbial liquid for use, significantly improving the deodorizing and odor-removing effect and application stability of the preparation, and has broad application prospects.

[0005] The technical solution adopted in this invention is as follows:

[0006] This invention provides a deodorizing and odor-removing compound microbial preparation, comprising the following components by weight:

[0007] 10-20 parts modified adsorption carrier and 40-50 parts composite microbial culture.

[0008] Preferably, the compound microbial inoculum is produced by inoculating compound microorganisms into a culture medium solution and fermenting it; the compound microorganisms consist of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei*.

[0009] Preferably, the ratio of the number of plant-like lactobacillus, rhamnosus lactobacillus and casei-like lactobacillus is 1-3:1-3:3.

[0010] This invention utilizes the synergistic effect of *Lactobacillus plantarum* and *Lactobacillus rhamnosus* on *Lactobacillus casei*, based on their complementary metabolic functions and microecological regulation capabilities. *Lactobacillus plantarum* secretes lipases and proteases, thereby decomposing large organic molecules such as oils and proteins into smaller metabolic products, providing usable substrates for other beneficial bacteria, and simultaneously interrupting the decomposition pathways of malodorous precursors (such as sulfur-containing amino acids), reducing the generation of hydrogen sulfide and methanethiol. *Lactobacillus rhamnosus* efficiently utilizes complex sugars such as starch and cellulose to produce lactic acid and acetic acid, inhibiting the growth of odor-producing putrefactive bacteria and indirectly reducing the release of malodorous gases such as ammonia and hydrogen sulfide. *Lactobacillus casei* secretes extracellular enzymes to directly degrade malodorous gases, converting ammonia and hydrogen sulfide into harmless substances. On the one hand, the three microorganisms form a symbiotic biofilm through quorum sensing, occupy the dominant ecological niche on the carrier surface and in the environment, exclude the colonization of odor-producing bacteria, and reduce their metabolic malodorous products. On the other hand, through metabolic complementarity and substrate synergistic degradation, *Lactobacillus plantarum* decomposes macromolecular organic matter into intermediate products, which are then further metabolized into harmless substances by *Lactobacillus rhamnosus* and *Lactobacillus casei*, forming a closed loop of degradation-transformation-inhibition of harmful bacteria.

[0011] Preferably, the fermentation temperature is 32-37℃ and the time is 40-60h.

[0012] Preferably, the inoculum size of the compound microorganisms is 1.0 × 10⁻⁶. 5 -2.0×10 5 CFU / mL feed solution.

[0013] Preferred strains of *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were purchased from the China Industrial Microbial Culture Collection Center.

[0014] Preferably, the culture medium solution, by weight, comprises 3-5 parts glucose, 1-3 parts beef extract powder, 1-3 parts casein peptone, 0.5-1.5 parts yeast extract powder, 0.5-1.5 parts sodium acetate, 0.2-0.6 parts triammonium citrate, 0.2-0.6 parts dipotassium hydrogen phosphate, 0.1-0.3 parts Tween 80, 0.02-0.06 parts magnesium sulfate, and 150-250 parts water.

[0015] Preferably, the method for preparing the culture medium solution is as follows:

[0016] Glucose, beef extract powder, casein peptone, yeast extract powder, sodium acetate, triammonium citrate, dipotassium hydrogen phosphate, Tween 80, magnesium sulfate and water are mixed, sterilized and cooled to room temperature to obtain the culture medium solution.

[0017] Preferably, the sterilization temperature is 115-121℃ and the time is 15-30 min.

[0018] Preferably, the modified adsorbent carrier is prepared by:

[0019] Dimethyl terephthalate, hydrazine hydrate, p-toluenesulfonic acid, and dimethyl sulfoxide were mixed, heated, cooled, filtered, washed, and dried to obtain a porous organic framework. The porous organic framework, trimellitic anhydride, and dimethyl sulfoxide were mixed, and then tetraethyl orthosilicate was added. The mixture was heated, cooled, filtered, washed, and dried to obtain a hybrid framework material.

[0020] The hybrid framework material was mixed with an aqueous solution of ferric nitrate, stirred, allowed to stand, filtered, and dried to obtain an iron-supported carrier. Polyethylene glycol and an aqueous solution of manganese nitrate were mixed, and then the iron-supported carrier was added. The mixture was sonicated, allowed to stand, filtered, dried, calcined, and cooled to obtain a composite carrier. Dopamine and Tris buffer were mixed, stirred, and then the composite carrier was added. The mixture was stirred, filtered, washed, and dried to obtain a modified adsorption carrier.

[0021] The modified adsorbent carrier prepared by the above method significantly improves the deodorizing and odor-removing effects, environmental adaptability, and stability of microbial preparations from the aspects of physical adsorption, chemical catalysis, and functional synergistic coupling. First, the porous organic framework can efficiently adsorb malodorous gases, while its high specific surface area helps provide dense attachment sites for beneficial bacteria. The SiO2-organic hybrid layer formed after silicon-oxygen network reinforcement treatment can seal the micropore defects of the porous organic framework. The carboxylic acid groups on the carrier surface adsorb ammonia through hydrogen bonding, and the amino groups fix hydrogen sulfide through acid-base neutralization, forming a dual chemical adsorption. Second, the calcined iron nitrate and manganese nitrate form a metal oxide catalytic system that can accelerate the conversion of malodorous gases into harmless substances, such as Fe. 3+ It can catalyze the generation of ·OH radicals to decompose hydrogen sulfide, Mn3+ Catalytic generation of O2 - It decomposes methanethiol and other substances; furthermore, polyethylene glycol acts as a heat stabilizer, maintaining the stability of the porous structure through a template effect. Finally, dopamine self-polymerizes under alkaline conditions to form a uniform coating on the carrier surface, which not only promotes the adhesion of beneficial bacteria and achieves high-strength anchoring, but also isolates metals with low toxicity. In summary, the modified adsorbent carrier of this invention, through its hierarchical porous structure, enhances the deodorization and odor removal effect while ensuring the long-term stability of the microbial preparation in complex environments.

[0022] Preferably, the weight ratio of dimethyl terephthalate, hydrazine hydrate, and p-toluenesulfonic acid is 10-15:15-20:0.1-0.3.

[0023] Preferably, the weight ratio of the porous organic framework, trimellitic anhydride, and tetraethyl orthosilicate is 5-10:10-15:1-2.

[0024] Preferably, the weight ratio of the hybrid framework material to the ferric nitrate aqueous solution is 5-15:100-200.

[0025] Preferably, the weight ratio of polyethylene glycol, manganese nitrate aqueous solution, and iron load carrier is 5-10:100-200:5-15.

[0026] Preferably, the weight ratio of dopamine to the composite carrier is 0.04-0.06:5-15.

[0027] Preferably, the modified adsorbent carrier is prepared by:

[0028] By weight, 10-15 parts of dimethyl terephthalate, 15-20 parts of hydrazine hydrate, 0.1-0.3 parts of p-toluenesulfonic acid, and 200-400 parts of dimethyl sulfoxide are mixed and reacted at 110-120℃ under a nitrogen atmosphere for 15-20 hours. After cooling to room temperature, the mixture is filtered, washed, and dried to obtain a porous organic framework. 5-10 parts of the porous organic framework, 10-15 parts of trimellitic anhydride, and 150-300 parts of dimethyl sulfoxide are mixed, and then 1-2 parts of tetraethyl orthosilicate are added. The mixture is stirred and reacted at 150-160℃ under a nitrogen atmosphere for 15-20 hours. After cooling to room temperature, the mixture is filtered, washed, and dried to obtain a hybrid framework material.

[0029] Mix 5-15 parts of hybrid framework material with 100-200 parts of ferric nitrate aqueous solution, stir at 22-27℃ for 0.5-1.5 h, then let stand for 1-3 h, filter, and dry to obtain an iron-supported carrier; mix 5-10 parts of polyethylene glycol with 100-200 parts of manganese nitrate aqueous solution, then add 5-15 parts of iron-supported carrier, sonicate for 20-30 min, let stand for 1-2 h, filter, dry, calcine under nitrogen atmosphere for 1-2 h, and cool to room temperature to obtain a composite carrier; mix 0.04-0.06 parts of dopamine with 200-300 parts of Tris buffer, stir at 22-27℃ for 40-60 min, then add 5-15 parts of composite carrier and continue stirring for 3-5 h, filter, wash, and dry to obtain a modified adsorption carrier.

[0030] Preferably, the polyethylene glycol is any one of polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000.

[0031] Preferably, the stirring speed is 150-450 r / min.

[0032] Preferably, the concentration of the ferric nitrate aqueous solution is 1-2 wt%.

[0033] Preferably, the concentration of the manganese nitrate aqueous solution is 2-5 wt%.

[0034] Preferably, the concentration of the Tris buffer solution is 0.04-0.06M and the pH is 8.0-9.0.

[0035] Preferably, the frequency of the ultrasound is 30-50kHz and the power is 150-300W.

[0036] Preferably, the calcination temperature is 250-300℃.

[0037] This invention also provides a method for preparing the above-mentioned deodorizing and odor-removing compound microbial preparation, comprising the following steps:

[0038] The modified adsorption carrier and the composite microbial liquid are mixed evenly to obtain the deodorizing and odor-removing composite microbial preparation.

[0039] This invention also provides the application of the above-mentioned deodorizing and odor-removing compound microbial preparation in deodorizing and odor-removing places such as toilets, domestic waste, and livestock pens.

[0040] Preferably, in the application of deodorizing and removing odors from toilet septic tanks, the deodorizing and odor-removing compound microbial preparation is diluted 10-30 times and sprayed at a rate of 10-30 mL / m³. 2 .

[0041] Preferably, in the application of deodorizing and removing odors from household waste, the deodorizing and odor-removing compound microbial preparation is diluted 10-30 times and sprayed at a rate of 10-30 mL / m³. 2 .

[0042] Preferably, in the application of deodorizing and removing odors in livestock and poultry pens, the deodorizing and odor-removing compound microbial preparation is diluted 10-30 times and sprayed at a rate of 20-40 mL / m². 2 .

[0043] The beneficial effects of this invention are:

[0044] This invention provides a deodorizing and odor-removing composite microbial preparation. By adding a modified adsorbent carrier made of a hybrid framework material that has been impregnated with metal salts twice, calcined, and coated with polydopamine, the preparation works synergistically with a composite microbial agent composed of plant-like lactobacillus, rhamnosus lactobacillus, and casei-like lactobacillus. This further enhances the deodorizing and odor-removing effects of the microbial preparation. It has the advantages of strong environmental adaptability, high application stability, and simple preparation process. Detailed Implementation

[0045] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] Example 1

[0047] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0048] By weight, 4 parts glucose, 2 parts beef extract powder, 2 parts casein peptone, 1 part yeast extract powder, 1 part sodium acetate, 0.4 parts triammonium citrate, 0.4 parts dipotassium hydrogen phosphate, 0.2 parts Tween 80, 0.04 parts magnesium sulfate, and 200 parts water were mixed and sterilized at 121°C for 15 minutes. The mixture was then cooled to room temperature to obtain the culture medium solution. The composite microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the composite microbial inoculum solution.

[0049] 15 parts of modified adsorption carrier and 45 parts of composite microbial inoculum were mixed evenly to obtain the deodorizing and odor-removing composite microbial preparation. The inoculum size of the composite microorganisms was 1.4 × 10⁻⁶. 5The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 2:2:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0050] The method for preparing the modified adsorbent carrier is as follows:

[0051] By weight, 12 parts of dimethyl terephthalate, 18 parts of hydrazine hydrate, 0.2 parts of p-toluenesulfonic acid, and 300 parts of dimethyl sulfoxide were mixed and stirred at 115°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a porous organic framework. 8 parts of the porous organic framework, 12 parts of trimellitic anhydride, and 200 parts of dimethyl sulfoxide were mixed, and then 1.5 parts of tetraethyl orthosilicate were added. The mixture was stirred at 155°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a hybrid framework material.

[0052] Ten parts of hybrid framework material and 150 parts of 1.5wt% ferric nitrate aqueous solution were mixed and stirred at 25℃ and 200r / min for 1h, then allowed to stand for 2h, filtered, and dried to obtain an iron-supported carrier. Eight parts of polyethylene glycol 4000 and 150 parts of 3.5wt% manganese nitrate aqueous solution were mixed and then 10 parts of iron-supported carrier were added. The mixture was sonicated at 40kHz and 200W for 25min, allowed to stand for 1.5h, filtered, dried, calcined at 280℃ under nitrogen atmosphere for 1.5h, and cooled to room temperature to obtain a composite carrier. 0.05 parts of dopamine and 250 parts of Tris buffer (concentration 0.05M, pH 8.5) were mixed and stirred at 25℃ and 400r / min for 50min. Ten parts of composite carrier were added and stirring was continued for 4h. The mixture was filtered, washed, and dried to obtain a modified adsorption carrier.

[0053] Example 2

[0054] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0055] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 32°C for 60 hours to obtain the compound microbial broth. Ten parts of modified adsorption carrier and 40 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.0 × 10⁻⁶. 5The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 1:1:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0056] The culture medium solution is the same as in Example 1; the modified adsorption carrier is the same as in Example 1.

[0057] Example 3

[0058] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0059] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 37°C for 40 hours to obtain the compound microbial broth. 20 parts of modified adsorption carrier and 50 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 2.0 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 3:3:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0060] The culture medium solution is the same as in Example 1; the modified adsorption carrier is the same as in Example 1.

[0061] Example 4

[0062] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0063] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the compound microbial broth. 15 parts of the modified adsorption carrier and 45 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.4 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microorganism composed of *Lactobacillus plantarum* and *Lactobacillus casei* in a ratio of 4:3. The strain number of *Lactobacillus plantarum* is CICC 24809, and the strain number of *Lactobacillus casei* is CICC 24946. Both were purchased from the China Industrial Microbial Culture Collection Center.

[0064] The culture medium solution is the same as in Example 1; the modified adsorption carrier is the same as in Example 1.

[0065] Example 5

[0066] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0067] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the compound microbial broth. 15 parts of the modified adsorption carrier and 45 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.4 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microorganism composed of *Lactobacillus rhamnosus* and *Lactobacillus casei* in a ratio of 4:3. The strain number of *Lactobacillus rhamnosus* is CICC6142, and the strain number of *Lactobacillus casei* is CICC24946. Both were purchased from the China Industrial Microbial Culture Collection Center.

[0068] The culture medium solution is the same as in Example 1; the modified adsorption carrier is the same as in Example 1.

[0069] Example 6

[0070] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0071] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the compound microbial broth. 15 parts of the modified adsorption carrier and 45 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.4 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 2:2:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0072] The culture medium solution is the same as in Example 1.

[0073] The method for preparing the modified adsorbent carrier is as follows:

[0074] By weight, 12 parts of dimethyl terephthalate, 18 parts of hydrazine hydrate, 0.2 parts of p-toluenesulfonic acid and 300 parts of dimethyl sulfoxide were mixed and stirred at 115°C, 200 r / min and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed and dried to obtain a porous organic framework.

[0075] Ten parts of porous organic framework and 150 parts of 1.5wt% ferric nitrate aqueous solution were mixed and stirred at 25℃ and 200r / min for 1h, then allowed to stand for 2h, filtered, and dried to obtain an iron-supported carrier. Eight parts of polyethylene glycol 4000 and 150 parts of 3.5wt% manganese nitrate aqueous solution were mixed and then 10 parts of iron-supported carrier were added. The mixture was sonicated at 40kHz and 200W for 25min, allowed to stand for 1.5h, filtered, dried, calcined at 280℃ under nitrogen atmosphere for 1.5h, and cooled to room temperature to obtain a composite carrier. 0.05 parts of dopamine and 250 parts of Tris buffer (concentration 0.05M, pH 8.5) were mixed and stirred at 25℃ and 400r / min for 50min. Ten parts of composite carrier were added and stirring was continued for 4h. The mixture was filtered, washed, and dried to obtain a modified adsorption carrier.

[0076] Example 7

[0077] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0078] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the compound microbial broth. 15 parts of the modified adsorption carrier and 45 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.4 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 2:2:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0079] The culture medium solution is the same as in Example 1.

[0080] The method for preparing the modified adsorbent carrier is as follows:

[0081] By weight, 12 parts of dimethyl terephthalate, 18 parts of hydrazine hydrate, 0.2 parts of p-toluenesulfonic acid, and 300 parts of dimethyl sulfoxide were mixed and stirred at 115°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a porous organic framework. 8 parts of the porous organic framework, 12 parts of trimellitic anhydride, and 200 parts of dimethyl sulfoxide were mixed, and then 1.5 parts of tetraethyl orthosilicate were added. The mixture was stirred at 155°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a hybrid framework material.

[0082] 0.05 parts of dopamine and 250 parts of Tris buffer (concentration of 0.05M, pH 8.5) were mixed and stirred at 25℃ and 400r / min for 50min. Then, 10 parts of hybrid framework material were added and stirring was continued for 4h. The mixture was filtered, washed, and dried to obtain the modified adsorption carrier.

[0083] Example 8

[0084] A method for preparing a deodorizing and odor-eliminating compound microbial agent includes the following steps:

[0085] By weight, the compound microorganisms were inoculated into the culture medium solution and fermented at 35°C for 48 hours to obtain the compound microbial broth. 15 parts of the modified adsorption carrier and 45 parts of the compound microbial broth were mixed evenly to obtain the deodorizing and odor-removing compound microbial preparation. The inoculation amount of the compound microorganisms was 1.4 × 10⁻⁶. 5 The CFU / mL feed solution contains a composite microbial mixture composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 2:2:3. The strain numbers for *Lactobacillus plantarum* (CICC 24809), *Lactobacillus rhamnosus* (CICC 6142), and *Lactobacillus casei* (CICC 24946) were all purchased from the China Industrial Microbial Culture Collection Center.

[0086] The culture medium solution is the same as in Example 1.

[0087] The method for preparing the modified adsorbent carrier is as follows:

[0088] By weight, 12 parts of dimethyl terephthalate, 18 parts of hydrazine hydrate, 0.2 parts of p-toluenesulfonic acid, and 300 parts of dimethyl sulfoxide were mixed and stirred at 115°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a porous organic framework. 8 parts of the porous organic framework, 12 parts of trimellitic anhydride, and 200 parts of dimethyl sulfoxide were mixed, and then 1.5 parts of tetraethyl orthosilicate were added. The mixture was stirred at 155°C, 200 r / min, and nitrogen atmosphere for 18 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a hybrid framework material.

[0089] Ten parts of hybrid framework material and 150 parts of 1.5wt% ferric nitrate aqueous solution were mixed and stirred at 25℃ and 200r / min for 1h, then allowed to stand for 2h, filtered, and dried to obtain an iron-supported carrier. Eight parts of polyethylene glycol 4000 and 150 parts of 3.5wt% manganese nitrate aqueous solution were mixed and then 10 parts of iron-supported carrier were added. The mixture was sonicated at 40kHz and 200W for 25min, allowed to stand for 1.5h, filtered, dried, calcined at 280℃ under nitrogen atmosphere for 1.5h, and cooled to room temperature to obtain a modified adsorption carrier.

[0090] Test Example 1

[0091] The deodorizing and odor-eliminating compound microbial preparations prepared in Examples 1-8 were diluted 15 times with water and then evenly sprayed into the enclosed bathroom at a rate of 20 mL / m². 2 The treatment period was 2 days. The concentrations of ammonia, hydrogen sulfide, and methanethiol in the bathroom were measured using a gas detector at the beginning and end of the treatment, and the removal rate was calculated. Removal rate = (initial gas concentration - final gas concentration) / initial gas concentration × 100%. The test results are shown in Table 1.

[0092]

[0093] The tests above show that the composite microbial preparations prepared in Examples 1-3 of this invention have the best deodorizing and odor-removing effects, and can efficiently remove malodorous gases. Compared with Examples 1-3, Examples 4-5 did not use the synergistic effect of *Lactobacillus plantarum* or *Lactobacillus rhamnosus* and *Lactobacillus casei*, and Examples 6-8 did not use specific modified adsorption carriers, resulting in varying degrees of decrease in the removal rate of the corresponding microbial preparations for various malodorous gases. It is evident that the composite microbial preparations prepared in Examples 1-3 utilize the synergistic effect of three microorganisms, which not only form a symbiotic relationship occupying a dominant ecological niche on the carrier surface and in the environment, excluding the colonization of odor-producing bacteria and reducing their metabolic malodorous products, but also form a closed loop of degradation-transformation-inhibition of harmful bacteria through metabolic complementarity and substrate synergistic degradation. Furthermore, the addition of modified adsorption carriers significantly improves the deodorizing and odor-removing effect, environmental adaptability, and stability of the microbial preparations from the aspects of physical adsorption, chemical catalysis, and functional synergistic coupling.

[0094] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A deodorizing and odor-eliminating compound microbial preparation, characterized in that, By weight, it comprises the following components: 10-20 parts of modified adsorption carrier and 40-50 parts of composite microbial culture solution; the composite microbial culture solution is prepared by fermenting composite microorganisms into a culture medium solution; the composite microorganisms are composed of *Lactobacillus plantarum*, *Lactobacillus rhamnosus*, and *Lactobacillus casei* in a ratio of 1-3:1-3:3; the strain number of *Lactobacillus plantarum* is CICC 24809, the strain number of *Lactobacillus rhamnosus* is CICC 6142, and the strain number of *Lactobacillus casei* is CICC24946; The method for preparing the modified adsorbent carrier is as follows: By weight, 10-15 parts of dimethyl terephthalate, 15-20 parts of hydrazine hydrate, 0.1-0.3 parts of p-toluenesulfonic acid, and 200-400 parts of dimethyl sulfoxide are mixed and reacted at 110-120℃ under a nitrogen atmosphere for 15-20 hours. After cooling to room temperature, the mixture is filtered, washed, and dried to obtain a porous organic framework. 5-10 parts of the porous organic framework, 10-15 parts of trimellitic anhydride, and 150-300 parts of dimethyl sulfoxide are mixed, and then 1-2 parts of tetraethyl orthosilicate are added. The mixture is stirred and reacted at 150-160℃ under a nitrogen atmosphere for 15-20 hours. After cooling to room temperature, the mixture is filtered, washed, and dried to obtain a hybrid framework material. Mix 5-15 parts of hybrid framework material with 100-200 parts of ferric nitrate aqueous solution, stir at 22-27℃ for 0.5-1.5 h, then let stand for 1-3 h, filter, and dry to obtain an iron-supported carrier; mix 5-10 parts of polyethylene glycol with 100-200 parts of manganese nitrate aqueous solution, then add 5-15 parts of iron-supported carrier, sonicate for 20-30 min, let stand for 1-2 h, filter, dry, calcine under nitrogen atmosphere for 1-2 h, and cool to room temperature to obtain a composite carrier; mix 0.04-0.06 parts of dopamine with 200-300 parts of Tris buffer, stir at 22-27℃ for 40-60 min, then add 5-15 parts of composite carrier and continue stirring for 3-5 h, filter, wash, and dry to obtain a modified adsorption carrier.

2. The deodorizing and odor-removing compound microbial preparation according to claim 1, characterized in that, The polyethylene glycol is any one of polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000.

3. The deodorizing and odor-removing compound microbial preparation according to claim 1, characterized in that, The inoculum size of the compound microorganisms was 1.0 × 10⁻⁶. 5 -2.0×10 5 The fermentation temperature was 32-37℃ and the fermentation time was 40-60h.

4. The deodorizing and odor-removing compound microbial preparation according to claim 1, characterized in that, The preparation method of the culture medium solution is as follows: Glucose, beef extract powder, casein peptone, yeast extract powder, sodium acetate, triammonium citrate, dipotassium hydrogen phosphate, Tween 80, magnesium sulfate, and water are mixed, sterilized, and cooled to obtain the culture medium solution.

5. The method for preparing the deodorizing and odor-removing compound microbial preparation according to any one of claims 1-4, characterized in that, Includes the following steps: The modified adsorption carrier and the composite microbial liquid are mixed evenly to obtain the deodorizing and odor-removing composite microbial preparation.

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