Microbial deodorant and production process thereof

Abstract

The invention provides a microbial deodorant and a production process thereof, and relates to the technical field of deodorants. The microbial deodorant is prepared from the following raw materials: 40 to 45 parts of a pyroligneous liquor-ferrous citrate compound, 7 to 10 parts of a lactobacillus plantarum microbial agent, 6 to 8 parts of a lactobacillus acidophilus microbial agent, 3 to 5 parts of a bacillus licheniformis microbial agent, 2 to 3 parts of a clostridium butyricum microbial agent and 19 to 24 parts of carrageenan nano microspheres. The pyroligneous liquor-ferrous citrate compound is prepared by the following steps: adding NaHCO3 into pyroligneous liquor to adjust the pH value to be weakly acidic to obtain pretreated pyroligneous liquor, then adding a ferrous citrate solution into the pretreated pyroligneous liquor, and reacting to obtain the pyroligneous liquor-ferrous citrate compound; the carrageenan nano-microsphere is prepared from the following raw material components: sophora flower polysaccharide, carrageenan, an emulsifier, paraffin and CaCl2. The microbial deodorant disclosed by the invention has excellent deodorization performance and relatively high stability.

Description

Technical Field

[0001] The present invention relates to the technical field of microbial deodorization, in particular to a microbial deodorant and a production process thereof. Background Art

[0002] With the rapid development of industrialized farming around the world, the problem of malodorous gases generated by livestock and poultry manure and wastewater discharge has become increasingly prominent. Malodorous gases such as ammonia and hydrogen sulfide not only affect the air quality and residents' lives around the farms, but also endanger the health of animals and reduce their production performance, such as reducing feed intake, weight loss, and affecting reproductive capacity. At the same time, long-term exposure may also damage the health of breeders.

[0003] Traditional deodorization methods mainly include physical adsorption and chemical deodorization. Physical adsorption methods (such as activated carbon and zeolite) temporarily reduce odors through surface adsorption, but cannot completely decompose malodorous substances. After adsorption saturation, they need to be frequently replaced, which is costly. Chemical deodorization methods (such as sodium hypochlorite and hydrogen peroxide) can quickly neutralize odors, but they are prone to secondary pollution and are irritating to the respiratory tract and skin of livestock and poultry. Long-term use may also disrupt the microecological balance of the breeding environment. In contrast, microbial deodorants have significant advantages. They are based on the principle that the metabolic activities of microorganisms can degrade malodorous substances. They are an environmentally friendly deodorization method that does not produce secondary pollution, meets the requirements of sustainable development, and are low in cost, which can effectively reduce breeding costs. At the same time, they also help improve animal growth performance and product quality. They are also safe and have no toxic side effects on humans or animals.

[0004] The types of microbial deodorants mainly include single strains and composite strains. Single strains, such as lactic acid bacteria and Bacillus, have specific functions but relatively narrow adaptability; composite strains are composed of a variety of microorganisms, such as lactic acid bacteria, yeast, Bacillus, etc., which can achieve synergistic effects and further improve deodorization performance. The prior art with publication number CN118909845A discloses a microbial deodorant for farms and a preparation method, which adopts a combination of multiple strains such as Bacillus subtilis, Bacillus licheniformis, and lactic acid bacteria, combined with an enzyme active agent composed of sulfide hydroxide oxidase and protease, and has a significant effect on the removal of ammonia and hydrogen sulfide. However, there are still problems such as limited regulation ability in acidic environment, insufficient ability to continuously decompose complex malodorous substances, and poor stability.

[0005] In summary, although the existing technical solutions have studied and improved microbial deodorants to a certain extent, the following technical problems still exist: the deodorizing performance of microbial deodorants is poor and the stability is low. Summary of the Invention

[0006] In order to solve the above problems existing in the prior art, the present application provides a microbial deodorant and a production process thereof, and achieves the following purposes: a microbial deodorant with excellent deodorizing performance and high stability is prepared.

[0007] In order to achieve the above-mentioned purposes, the technical scheme adopted is as follows: A microbial deodorant, the raw material composition of which comprises, in parts by weight, 40-45 parts of wood vinegar-citric acid ferrous compound, 7-10 parts of lactobacillus plantarum agent, 6-8 parts of lactobacillus acidophilus agent, 3-5 parts of bacillus licheniformis agent, 2-3 parts of butyric acid clostridium agent and 19-24 parts of carrageenan nanometer microspheres.

[0008] The raw material components of the carrageenan nanometer microspheres comprise sophora flower polysaccharide, carrageenan, emulsifier, paraffin and CaCl2.

[0009] The wood vinegar-citric acid ferrous compound is prepared by adding NaHCO3 into wood vinegar to adjust the pH value to weak acidity to obtain pretreated wood vinegar, and then adding a citric acid ferrous solution into the pretreated wood vinegar to obtain the wood vinegar-citric acid ferrous compound.

[0010] The sophora flower polysaccharide has a purity greater than 75%.

[0011] The carrageenan has a purity greater than 90% and a viscosity greater than 200 mPa・s.

[0012] The present application further provides a production process of the microbial deodorant, and the steps are as follows: Step one, preparation of wood vinegar-citric acid ferrous compound NaHCO3 is added into wood vinegar under stirring at 100-150 rpm to adjust the pH value of the wood vinegar to 5.5-6.5 to obtain pretreated wood vinegar.

[0013] Step two, synthesis of carrageenan nanometer microspheres Sophora japonica polysaccharide is prepared into a 5.2-5.8 mg / mL concentration of a Sophora japonica polysaccharide solution. The Sophora japonica polysaccharide solution and carrageenan are mixed, heated to 60-70°C to dissolve, and then cooled to room temperature to obtain a mixture A. Tween-80 emulsifier is added to the mixture A and stirred at 2000-3000 rpm for 5-10 minutes. Liquid paraffin is then added to the mixture A and stirred at 8000-10000 rpm for 10-15 minutes to form an emulsion.

[0014] Prepare a 0.1-0.15 mol / L CaCl2 solution. Add the CaCl2 solution dropwise to the emulsion, with the volume of the CaCl2 solution accounting for 5%-10% of the volume of Mixture A. Stir at 300-400 rpm for 40-60 minutes, then centrifuge at 6000-7000 rpm for 10-15 minutes. Discard the supernatant to obtain carrageenan nanospheres.

[0015] The mass ratio of Sophora japonica polysaccharide solution to carrageenan is (12-16):7; the mass ratio of Tween-80 emulsifier to mixture A is (5-7):100; and the volume ratio of mixture A to liquid paraffin is 1:(3-5).

[0016] Step 3: Carrageenan nanospheres loaded with microbial agents Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum are cultured separately to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum; then the Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum are mixed evenly to obtain a bacterial suspension; carrageenan nanospheres are dispersed in the bacterial suspension, and the suspension is adsorbed at 32-35°C for 2-2.5 hours with an oscillation speed set at 150-200 rpm; then the suspension is centrifuged at 1000-2000 rpm for 10-15 minutes, and the supernatant is discarded to obtain loaded bacterial microspheres.

[0017] The bacterial content of Lactobacillus plantarum is 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×10 9 -3.8×10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculum was 1.5×10 9 -1.9×10 9 CFU / g, the bacterial content of Clostridium butyricum agent was 1.0×10 9 -1.3×10 9 CFU / g.

[0018] Step 4: Prepare microbial deodorant The loaded microspheres and the wood vinegar-ferrous citrate complex are added to a biaxial paddle mixer, the speed is set to 30-50 rpm, and the stirring time is 10-15 minutes to obtain a mixture. Then, vacuum freeze drying is performed. The mixture is placed in a freeze dryer, the temperature is set to -40°C to -50°C, and maintained for 2-3 hours. The vacuum pump is turned on, the pressure is set to 10-30 Pa, and the temperature is slowly increased to -10°C to 5°C at a heating rate of 0.5-1°C / h, and maintained for 12-24 hours. The temperature is further increased to 20-30°C at a heating rate of 1-2°C / h and dried for 4-6 hours. The freeze-dried material is ground into a powder and passed through an 80-mesh sieve to obtain a microbial deodorant.

[0019] The Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum described in the present invention are all commercially available.

[0020] The beneficial effects of the present invention are as follows: (1) The microbial deodorant of the present invention has excellent deodorizing performance. The NH3 removal rate reaches 68.95-71.42% in 0.5 h, 91.73-93.44% in 1 h, and 94.85-95.61% in 2 h. The H2S removal rate reaches 79.73-82.59% in 0.5 h, 92.46-93.87% in 1 h, and 96.59-98.35% in 2 h.

[0021] (2) The microbial deodorant of the present invention has excellent stability. After 18 months of storage, the number of viable bacteria can still reach 7.56×10 9 -9.51×10 9 CFU / g, with a decrease rate of 20.2%-23.3%, indicating that the wood vinegar-ferrous citrate complex and the carrageenan microspheres doped with Sophora japonica polysaccharide significantly improved the survival rate of the microbial agent and enhanced the stability of the microbial deodorant prepared by the present invention. DETAILED DESCRIPTION

[0022] To make the purpose, technical solutions and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0023] Example 1 A microbial deodorant and its production process A microbial deodorant comprises the following raw materials, measured in parts by weight: 40 parts of wood vinegar-ferrous citrate complex, 10 parts of Lactobacillus plantarum agent, 8 parts of Lactobacillus acidophilus agent, 5 parts of Bacillus licheniformis agent, 3 parts of Clostridium butyricum agent, and 24 parts of carrageenan nanospheres.

[0024] A production process of a microbial deodorant comprises the following steps: Step 1: Preparation of Wood Vinegar-Ferrous Citrate Complex NaHCO₃ was added to the wood vinegar solution while stirring at 100 rpm to adjust the pH of the wood vinegar solution to 5.5, thereby obtaining a pretreated wood vinegar solution. Ferrous citrate was dissolved in deionized water to prepare a 0.2 mol / L ferrous citrate solution, which was then added to the pretreated wood vinegar solution at a volume ratio of 3:1. The mixture was stirred at 150 rpm for 1.5 hours to obtain a wood vinegar-ferrous citrate complex. The wood vinegar solution contained greater than 50 g / L of organic acid.

[0025] Step 2: Synthesis of carrageenan nanospheres Sophora japonica polysaccharide was prepared into a 5.2 mg / mL concentration of a Sophora japonica polysaccharide solution. The Sophora japonica polysaccharide solution and carrageenan were mixed, heated to 70°C to dissolve, and then cooled to room temperature to obtain Mixture A. Tween-80 emulsifier was added to Mixture A and stirred at 2000 rpm for 5 minutes. Liquid paraffin was then added to Mixture A and stirred at 8000 rpm for 10 minutes to form an emulsion. The Sophora japonica polysaccharide had a purity greater than 75%. The carrageenan had a purity greater than 90% and a viscosity greater than 200 mPa·s. The mass ratio of the Sophora japonica polysaccharide solution to the carrageenan was 12:7; the mass ratio of the Tween-80 emulsifier to Mixture A was 7:100; and the volume ratio of Mixture A to the liquid paraffin was 1:3.

[0026] A 0.15 mol / L CaCl2 solution was prepared. The CaCl2 solution was added dropwise to the emulsion, with the volume of the CaCl2 solution accounting for 5% of the volume of Mixture A. The mixture was stirred at 300 rpm for 40 minutes, then centrifuged at 6000 rpm for 10 minutes, and the supernatant was discarded to obtain carrageenan nanospheres.

[0027] Step 3: Carrageenan nanospheres loaded with microbial agents Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis, and Clostridium butyricum were cultured in liquid respectively to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis, and Clostridium butyricum. Then, Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis, and Clostridium butyricum were mixed evenly in proportion to obtain a bacterial suspension. Carrageenan nanospheres were dispersed in the bacterial suspension, oscillated and adsorbed at 35°C for 2h, and the oscillation speed was set to 200rpm. Then, the mixture was centrifuged at 1000rpm for 15min, the supernatant was discarded, and the loaded bacterial microspheres were obtained. The bacterial content of the Lactobacillus plantarum agent was 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×10 9- 3.8 x 10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculant was 1.5 x 10 9 - 1.9 x 10 9 CFU / g, the bacterial content of Clostridium butyricum inoculant was 1.0 x 10 9 - 1.3 x 10 9 CFU / g.

[0028] Step four, a microbial deodorant is prepared The loaded bacterial microspheres and the wood vinegar-citrate ferrous complex are added to a double-shaft paddle mixer, the rotating speed is set to 30 rpm, and the stirring time is 15 min to obtain a mixture. Then, vacuum freeze drying is performed, the mixture is placed in a freeze dryer, the temperature is set to -40℃ and maintained for 3 h; the vacuum pump is started, the pressure is set to 10 Pa, the temperature is slowly increased to 5℃ at a rate of 0.5℃ / h, and maintained for 12 h; the temperature is continuously increased to 30℃ at a rate of 1℃ / h, and dried for 4 h. The freeze-dried material is ground into a powder, and passed through an 80-mesh sieve to obtain the microbial deodorant.

[0029] Example 2: A microbial deodorant and its production process A microbial deodorant, the raw material composition is as follows in terms of weight parts: wood vinegar-citrate ferrous complex 42 parts, Lactobacillus plantarum inoculant 8 parts, Lactobacillus acidophilus inoculant 7 parts, Bacillus licheniformis inoculant 3 parts, Clostridium butyricum inoculant 2 parts, and carrageenan nanometer microspheres 19 parts.

[0030] A production process of a microbial deodorant, the steps are as follows: Step one, preparation of wood vinegar-citrate ferrous complex Under stirring at 150 rpm, NaHCO3 is added to the wood vinegar to adjust the pH value of the wood vinegar to 6 to obtain pretreated wood vinegar. Citrate ferrous is dissolved in deionized water to prepare a 0.3 mol / L citrate ferrous solution, and then the citrate ferrous solution is added to the pretreated wood vinegar, the volume ratio of the pretreated wood vinegar to the citrate ferrous solution is 4:1, and stirring is performed at 200 rpm for 1.5 h to obtain the wood vinegar-citrate ferrous complex. The organic acid content of the wood vinegar is greater than 50 g / L.

[0031] Step two, synthesis of carrageenan nanometer microspheres Sophora japonica polysaccharide was prepared into a 5.8 mg / mL concentration of a Sophora japonica polysaccharide solution. The Sophora japonica polysaccharide solution and carrageenan were mixed, heated to 65°C to dissolve, and then cooled to room temperature to obtain Mixture A. Tween-80 emulsifier was added to Mixture A and stirred at 3000 rpm for 10 minutes. Liquid paraffin was then added to Mixture A and stirred at 9000 rpm for 12 minutes to form an emulsion. The Sophora japonica polysaccharide had a purity greater than 75%. The carrageenan had a purity greater than 90% and a viscosity greater than 200 mPa·s. The mass ratio of the Sophora japonica polysaccharide solution to the carrageenan was 15:7; the mass ratio of the Tween-80 emulsifier to Mixture A was 3:50; and the volume ratio of Mixture A to the liquid paraffin was 1:4.

[0032] A 0.1 mol / L CaCl2 solution was prepared. The CaCl2 solution was added dropwise to the emulsion, with the volume of the CaCl2 solution accounting for 12% of the volume of Mixture A. The mixture was stirred at 300 rpm for 50 minutes, then centrifuged at 6000 rpm for 10 minutes, and the supernatant was discarded to obtain carrageenan nanospheres.

[0033] Step 3: Carrageenan nanospheres loaded with microbial agents Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were cultured in liquid respectively to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum. Then Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were mixed evenly in proportion to obtain a bacterial suspension. Carrageenan nanospheres were dispersed in the bacterial suspension and adsorbed at 32°C for 2h with an oscillation speed of 200rpm. Then the mixture was centrifuged at 2000rpm for 15min, the supernatant was discarded and the loaded bacterial microspheres were obtained. The bacterial content of the Lactobacillus plantarum agent was 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×10 9 -3.8×10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculum was 1.5×10 9 -1.9×10 9 CFU / g, the bacterial content of Clostridium butyricum agent was 1.0×10 9 -1.3×10 9 CFU / g.

[0034] Step 4: Prepare microbial deodorant The loaded microspheres and the wood vinegar-ferrous citrate complex were added to a biaxial paddle mixer at 40 rpm for 15 minutes to obtain a mixture. The mixture was then freeze-dried in a vacuum oven at -40°C for 3 hours. The vacuum pump was activated, the pressure set to 20 Pa, and the temperature was slowly increased to 5°C at a rate of 1°C / hour for 24 hours. The temperature was then increased to 25°C at a rate of 2°C / hour and dried for 6 hours. The freeze-dried material was ground into a powder and passed through an 80-mesh sieve to obtain a microbial deodorant.

[0035] Example 3 A microbial deodorant and its production process A microbial deodorant comprises the following raw materials, measured in parts by weight: 45 parts of wood vinegar-ferrous citrate complex, 7 parts of Lactobacillus plantarum agent, 6 parts of Lactobacillus acidophilus agent, 3 parts of Bacillus licheniformis agent, 2 parts of Clostridium butyricum agent, and 21 parts of carrageenan nanospheres.

[0036] A production process of a microbial deodorant comprises the following steps: Step 1: Preparation of Wood Vinegar-Ferrous Citrate Complex NaHCO₃ was added to the wood vinegar solution while stirring at 150 rpm to adjust the pH of the wood vinegar solution to 6.5, thereby obtaining a pretreated wood vinegar solution. Ferrous citrate was dissolved in deionized water to prepare a 0.4 mol / L ferrous citrate solution, which was then added to the pretreated wood vinegar solution at a volume ratio of 5:1. The mixture was stirred at 200 rpm for 1 hour to obtain a wood vinegar-ferrous citrate complex. The wood vinegar solution contained greater than 50 g / L of organic acid.

[0037] Step 2: Synthesis of carrageenan nanospheres Sophora japonica polysaccharide was prepared into a 5.4 mg / mL concentration of a Sophora japonica polysaccharide solution. The Sophora japonica polysaccharide solution and carrageenan were mixed, heated to 70°C to dissolve, and then cooled to room temperature to obtain Mixture A. Tween-80 emulsifier was added to Mixture A and stirred at 2000 rpm for 8 minutes. Liquid paraffin was then added to Mixture A and stirred at 10000 rpm for 10 minutes to form an emulsion. The Sophora japonica polysaccharide had a purity greater than 75%. The carrageenan had a purity greater than 90% and a viscosity greater than 200 mPa·s. The mass ratio of the Sophora japonica polysaccharide solution to the carrageenan was 16:7; the mass ratio of the Tween-80 emulsifier to Mixture A was 1:20; and the volume ratio of Mixture A to the liquid paraffin was 1:3.

[0038] A 0.1 mol / L CaCl2 solution was prepared. The CaCl2 solution was added dropwise to the emulsion, with the volume of the CaCl2 solution accounting for 5% of the volume of Mixture A. The mixture was stirred at 400 rpm for 60 minutes, then centrifuged at 7000 rpm for 10 minutes, and the supernatant was discarded to obtain carrageenan nanospheres.

[0039] Step 3: Carrageenan nanospheres loaded with microbial agents Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were cultured in liquid respectively to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum. Then Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were mixed evenly in proportion to obtain a bacterial suspension. Carrageenan nanospheres were dispersed in the bacterial suspension and adsorbed at 35°C for 2.5h with an oscillation speed of 150rpm. Then centrifuged at 8000rpm for 10min, the supernatant was discarded to obtain loaded bacterial microspheres. The bacterial content of the Lactobacillus plantarum agent was 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×10 9 -3.8×10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculum was 1.5×10 9 -1.9×10 9 CFU / g, the bacterial content of Clostridium butyricum agent was 1.0×10 9 -1.3×10 9 CFU / g.

[0040] Step 4: Prepare microbial deodorant The loaded microspheres and the wood vinegar-ferrous citrate complex were added to a biaxial paddle mixer at 50 rpm for 10 minutes to obtain a mixture. The mixture was then freeze-dried in a vacuum oven at -50°C for 2 hours. The vacuum pump was activated, the pressure set to 30 Pa, and the temperature was slowly raised to -10°C at a rate of 1°C / hour for 24 hours. The temperature was then raised to 20°C at a rate of 2°C / hour and dried for 6 hours. The freeze-dried material was ground into a powder and passed through an 80-mesh sieve to obtain a microbial deodorant.

[0041] Comparative Example 1 A microbial deodorant and its production process On the basis of Example 1, the wood vinegar-ferrous citrate complex is replaced with "wood vinegar", and the specific formula is: A microbial deodorant comprises the following raw materials, measured in parts by weight: 40 parts of wood vinegar, 10 parts of Lactobacillus plantarum, 8 parts of Lactobacillus acidophilus, 5 parts of Bacillus licheniformis, 3 parts of Clostridium butyricum, and 24 parts of carrageenan nanospheres.

[0042] A production process of a microbial deodorant comprises the following steps: Step 1: Synthesis of carrageenan nanospheres The steps are the same as those in “Synthesis of Carrageenan Nanospheres” in Example 1.

[0043] Step 2: Carrageenan nanospheres loaded with microbial agents The steps are the same as those in Example 1 for “carrageenan nanospheres loaded with microbial agents”.

[0044] Step 3: Prepare microbial deodorant The wood vinegar-ferrous citrate complex was replaced with "wood vinegar", and the other preparation methods were the same as the steps of "preparing the microbial deodorant" in Example 1.

[0045] Comparative Example 2 A microbial deodorant and its production process On the basis of Example 1, the carrageenan nanospheres were replaced with "carrageenan", and the specific formula was: A microbial deodorant comprises the following raw materials, measured in parts by weight: 40 parts of wood vinegar-ferrous citrate complex, 10 parts of Lactobacillus plantarum agent, 8 parts of Lactobacillus acidophilus agent, 5 parts of Bacillus licheniformis agent, 3 parts of Clostridium butyricum agent, and 24 parts of carrageenan.

[0046] A production process of a microbial deodorant comprises the following steps: Step 1: Preparation of Wood Vinegar-Ferrous Citrate Complex The steps are the same as those in Example 1 for the preparation of wood vinegar-ferrous citrate complex.

[0047] Step 2: Carrageenan loaded with microbial agents Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were cultured in liquid respectively to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum. Then Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum were mixed evenly in proportion to obtain a bacterial suspension. Carrageenan was dispersed in the bacterial suspension and adsorbed at 35°C for 2h with an oscillation speed of 200rpm. Then the mixture was centrifuged at 1000rpm for 15min, the supernatant was discarded and a bacterial liquid mixture was obtained. The bacterial content of the Lactobacillus plantarum was 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×109 -3.8 x 10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculant was 1.5 x 10 9 -1.9 x 10 9 CFU / g, the bacterial content of Clostridium butyricum inoculant was 1.0 x 10 9 -1.3 x 10 9 CFU / g.

[0048] Step four, preparing microbial deodorant The mixture of bacterial solution and wood vinegar-ferric citrate complex was added into a double-shaft paddle mixer, and the specific preparation process and parameters were the same as those in step of "preparing microbial deodorant" in Example 1.

[0049] Example 4, performance test (I) Deodorization rate test The microbial deodorants prepared in Examples 1-3 and Comparative Examples 1-2 were respectively dissolved in sterile water, and the mass ratio of microbial deodorant to sterile water was 1:100. After mixing and standing for 30 min, the supernatant was taken as the test solution. A certain amount of NH3 or H2S gas was introduced into a 10 L closed glass dryer, and the concentration was controlled by a gas flow meter. The initial concentration was set to 50 ppm NH3 and 10 ppm H2S. 1 L of the test solution was added to the glass dryer, and the reaction was carried out at room temperature for 1 h with a shaking speed of 150 rpm. The gas concentration before and after the reaction was detected by gas chromatography, and the removal rate was calculated. The removal rate (%) = [(initial gas concentration - post-reaction gas concentration) / initial gas concentration] x 100%. The test results are shown in Table 1.

[0050] Table 1 As shown in Table 1, the microbial deodorants prepared by the present application have excellent deodorizing performance. The NH3 removal rate reached 68.95-71.42% at 0.5 h, 91.73-93.44% at 1 h, and 94.85-95.61% at 2 h. The H2S removal rate reached 79.73-82.59% at 0.5 h, 92.46-93.87% at 1 h, and 96.59-98.35% at 2 h.

[0051] (II) Stability test The initial viable cell count and the viable cell count after 18 months of storage were detected according to the test method specified in GB 20287-2006. The storage condition was that the sample was placed in a sealed container and stored at 25℃±2℃ under light-proof condition. The viable cell count calculation was viable cell count (CFU / g)=(average number of colonies on the plate×dilution factor) / sample mass; the decrease rate calculation was decrease rate (%)=[(initial viable cell count-viable cell count after 18 months of storage) / initial viable cell count]×100%. The test results are shown in Table 2.

[0052] Table 2 It can be known from the test results in Table 2 that the microbial deodorant prepared in the application has excellent stability. The viable cell count can still reach 7.56×10 9 -9.51×10 9 CFU / g after 18 months of storage, and the decrease rate is 20.2%-23.3%, which indicates that the application significantly improves the survival rate of the microbial agent and the stability of the microbial deodorant.

[0053] The specific parameters of the microbial agent culture medium in the application are as follows: The culture medium of Lactobacillus plantarum and Lactobacillus acidophilus: glucose 20g / L, proteose peptone 10g / L, beef extract 10g / L, yeast extract 5g / L, diammonium citrate 2g / L, sodium acetate 5g / L, potassium phosphate dibasic 2g / L, magnesium sulfate 0.58g / L, manganese sulfate 0.25g / L, Tween-80 1mL / L; each component is dissolved in deionized water, constant volume to 1L, and the pH value is adjusted to 6.2-6.5 by NaOH or HCl, and sterilized at 120℃ for 20min.

[0054] The culture medium of Bacillus licheniformis: proteose peptone 10g / L, yeast extract 5g / L, sodium chloride 10g / L; each component is dissolved in deionized water, constant volume to 1L, and the pH value is adjusted to 7.0-7.2 by NaOH, and sterilized at 120℃ for 20min.

[0055] The culture medium of Clostridium butyricum: glucose 10g / L, proteose peptone 10g / L, yeast extract 5g / L, sodium chloride 5g / L, sodium acetate 3g / L, cysteine hydrochloride 0.5g / L; each component is dissolved in deionized water, constant volume to 1L, and the pH value is adjusted to 6.5-7.0 by NaOH or HCl, and nitrogen or argon is introduced to remove oxygen, and sterilized at 115℃ for 20min.

[0056] Obviously, there are still many specific implementation methods that can be changed under the concept of the application, and here it should be declared that any change made under the inventive concept of the application will fall within the protection scope of the application.

Claims

1. A microbial deodorant, characterized in that: The microbial deodorant comprises, in parts by weight, 40-45 parts of wood vinegar-ferrous citrate complex, 7-10 parts of Lactobacillus plantarum, 6-8 parts of Lactobacillus acidophilus, 3-5 parts of Bacillus licheniformis, 2-3 parts of Clostridium butyricum, and 19-24 parts of carrageenan nanospheres. The wood vinegar-ferrous citrate complex is prepared by adding NaHCO3 to the wood vinegar to adjust the pH value to be weakly acidic to obtain a pretreated wood vinegar solution, and then adding a ferrous citrate solution to the pretreated wood vinegar solution to react and obtain the wood vinegar-ferrous citrate complex; The raw material components of the carrageenan nanospheres include sophora japonica polysaccharide, carrageenan, emulsifier, paraffin and CaCl2.

2. A microbial deodorant according to claim 1, characterized in that: The volume ratio of the pretreated wood vinegar solution to the ferrous citrate solution is (3-5):

1.

3. The production process of a microbial deodorant according to any one of claims 1-2, characterized in that: The method comprises the steps of preparing a wood vinegar-ferrous citrate complex, synthesizing carrageenan nano-microspheres, loading microbial agents on the carrageenan nano-microspheres, and preparing a microbial deodorant. Preparation of the wood vinegar-ferrous citrate complex: adjusting the pH value of the wood vinegar to be weakly acidic to obtain a pretreated wood vinegar; Ferrous citrate is dissolved in deionized water to prepare a 0.2-0.4 mol / L ferrous citrate solution, and then the ferrous citrate solution is added to the pretreated wood vinegar; the volume ratio of the pretreated wood vinegar to the ferrous citrate solution is (3-5):1; the organic acid content of the wood vinegar is greater than 50 g / L.

4. A microbial deodorant according to claim 3, characterized in that: In the preparation step of the wood vinegar-ferrous citrate complex, the pH value of the wood vinegar is adjusted by adding NaHCO3 to the wood vinegar to adjust the pH value of the wood vinegar to 5.5-6.

5.

5. A microbial deodorant according to claim 3, characterized in that: The synthesis of the carrageenan nanospheres comprises the following steps: mixing a 5.2-5.8 mg / mL sophora japonica polysaccharide solution and carrageenan, heating the mixture to 60-70°C for dissolution, and then cooling the mixture to room temperature to obtain a mixture A; adding a Tween-80 emulsifier to the mixture A, stirring the mixture at a rate of 2000-3000 rpm for 5-10 minutes; adding liquid paraffin to the mixture A, stirring the mixture at a rate of 8000-10000 rpm for 10-15 minutes to form an emulsion; dropwise adding a 0.1-0.15 mol / L CaCl2 solution to the emulsion, wherein the volume of the CaCl2 solution accounts for 5%-10% of the volume of the mixture A; stirring the mixture at 300-400 rpm for 40-60 minutes, and then centrifuging the mixture at 6000-7000 rpm for 10-15 minutes, and discarding the supernatant to obtain the carrageenan nanospheres.

6. A microbial deodorant according to claim 5, characterized in that: In the synthesis step of the carrageenan nanospheres, the mass ratio of the sophora japonica polysaccharide solution to the carrageenan is (12-16):7; the mass ratio of the Tween-80 emulsifier to the mixture A is (5-7):100; and the volume ratio of the mixture A to the liquid paraffin is 1:(3-5).

7. A microbial deodorant according to claim 3, characterized in that: The carrageenan nanospheres are loaded with microbial agents. Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum are cultured separately to obtain Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum agents; the Lactobacillus plantarum, Lactobacillus acidophilus, Bacillus licheniformis and Clostridium butyricum agents are then uniformly mixed to obtain a bacterial suspension; the carrageenan nanospheres are dispersed in the bacterial suspension, and the suspension is oscillated and adsorbed at 32-35°C for 2-2.5 hours with an oscillation speed set at 150-200 rpm; and the suspension is centrifuged at 1000-2000 rpm for 10-15 minutes, and the supernatant is discarded to obtain the loaded microspheres.

8. A microbial deodorant according to claim 7, characterized in that: In the step of loading the microbial agent with carrageenan nanospheres, the bacterial content of the Lactobacillus plantarum agent is 4.5×10 9 -5.6×10 9 CFU / g, the bacterial content of Lactobacillus acidophilus agent was 3.0×10 9 -3.8×10 9 CFU / g, the bacterial content of Bacillus licheniformis inoculum was 1.5×10 9 -1.9×10 9 CFU / g, the bacterial content of Clostridium butyricum agent was 1.0×10 9 -1.3×10 9 CFU / g.

9. The microbial deodorant according to claim 3, characterized in that: The microbial deodorant is prepared by adding the loaded bacterial microspheres and the wood vinegar-ferrous citrate complex into a biaxial paddle mixer, setting the rotation speed to 30-50 rpm and stirring for 10-15 minutes to obtain a mixed material; then performing vacuum freeze drying, grinding the freeze-dried material into a powder, and passing it through an 80-mesh sieve to obtain the microbial deodorant.

10. A microbial deodorant according to claim 9, characterized in that: The vacuum freeze drying step of the microbial deodorant preparation step comprises: placing the mixed material into a freeze dryer, setting the temperature to -40°C to -50°C, and maintaining it for 2-3 hours; starting a vacuum pump, setting the pressure to 10-30 Pa, slowly heating the material to -10°C to 5°C at a heating rate of 0.5-1°C / h, and maintaining it for 12-24 hours; and continuing to heat the material to 20-30°C at a heating rate of 1-2°C / h, and drying the material for 4-6 hours.

Images