Deodorant for air disinfection and deodorization and preparation process thereof

Abstract

The invention provides a deodorant for air disinfection and deodorization and a preparation process thereof, and belongs to the technical field of air purification. Comprising the following components: a composite deodorizing material, a composite essential oil microcapsule, a surfactant, benzalkonium bromide and water. The preparation method comprises the following steps: mixing and dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate, adding hexadecyl trimethyl ammonium bromide and ammonia water to prepare a mesoporous nano-hydroxyapatite precursor suspension, adding a zinc nitrate solution, and carrying out hydrothermal reaction and calcination to prepare a composite carrier material; when the composite essential oil is loaded into the composite carrier material by using a vacuum impregnation method, the composite essential oil can have a slow release effect, the long-acting deodorization effect of the deodorant is improved, and more adsorption sites can be provided for the composite essential oil, so that the loading rate of the composite carrier material to the composite essential oil can be remarkably improved, and the deodorization effect of the deodorant is improved. The deodorization effect of the deodorant is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of air purification, and in particular to a deodorant for air disinfection and deodorization and a preparation process thereof. Background Art

[0002] Odor emissions are one of the serious problems of global air pollution, and animal husbandry is the main source. Large-scale odor emissions will not only cause a series of environmental problems such as acid rain, eutrophication of water bodies, soil acidification, global warming and reduction of biodiversity, but will also have adverse effects on human and animal health.

[0003] As one of the odor control technologies in livestock farms, deodorants can remove various pollutants that emit foul odors and harmful gases in the air of poultry houses. According to different mechanisms of action, deodorants can be divided into physical deodorants, chemical deodorants, microbial deodorants and plant deodorants. Physical deodorants mainly use adsorption and masking effects to achieve the purpose of deodorization. Commonly used materials for this type of deodorant include activated carbon, zeolite, aromatic compounds, etc., but the deodorizing materials need to be replaced or supplemented frequently; chemical deodorants use chemical reagents to react with odor molecules to achieve the purpose of deodorization. Its characteristics are rapid reaction but short-lasting effect, and easy to produce secondary pollution; plant deodorants are mainly a type of deodorant with plant extracts as active ingredients. Due to its wide source, natural pollution-free, high deodorization efficiency, good biodegradability, wide range of applications, and easy use, it is considered to be a type of deodorant with great development prospects.

[0004] The active ingredients such as polyphenols, terpenes, aldehydes, etc. in plant essential oils can undergo oxidation-reduction, acid-base neutralization, addition condensation and other reactions with odor molecules, changing the molecular structure of odors and generating non-toxic and odorless substances. The antibacterial ingredients can inhibit the growth of harmful microorganisms and achieve the purpose of air sterilization and disinfection. Therefore, plant essential oils, as a plant deodorant, are not only natural and pollution-free, but also have good air disinfection and deodorization effects. However, plant essential oils are volatile, and direct use will cause the deodorization effect to fail quickly, and the disinfection and deodorization effects will not last long.

[0005] In addition, current studies have shown that live microbial bacteria can absorb harmful gases such as ammonia and hydrogen sulfide, convert them into harmless substances through biochemical reactions, and degrade skatole, thereby reducing irritation to the respiratory tract and conjunctiva of livestock and poultry, reducing the incidence and mortality of diseases. Moreover, compared with free microorganisms, fixing microorganisms in carriers can keep the microorganisms highly dense in a limited spatial area and maintain their biological activity, thereby accelerating the rate at which microorganisms decompose odors.

[0006] Based on this, it is necessary to propose a deodorant for air disinfection and deodorization and a preparation process thereof to achieve a long-lasting deodorization effect. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide a deodorant for air disinfection and deodorization and a preparation process thereof.

[0008] A preparation process of a deodorant for air disinfection and deodorization comprises the following steps: S1: The porous starch is modified by using quaternized cellulose, and then Bacillus subtilis, Bacillus natto and Rhodococcus gordonii YKSW-6 are loaded with the modified porous starch to obtain a composite deodorizing material; S2: dissolving tetrahydrate nitric acid and diammonium hydrogen phosphate in deionized water, adding hexadecyltrimethylammonium bromide and zinc nitrate solution, mixing thoroughly, performing hydrothermal reaction, and calcining to obtain a composite carrier material; S3: using the composite carrier material to load the composite essential oil, adding it to a sodium dodecyl sulfate aqueous solution, stirring and mixing evenly, adding a sodium alginate aqueous solution and a chitosan solution, continuing to stir and mix, and adding a glutaraldehyde aqueous solution for cross-linking to obtain a composite essential oil microcapsule; S4: Mix the composite deodorant material, the composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and disperse them by ultrasonic for 1-2 hours to obtain a deodorant.

[0009] Furthermore, S1 specifically includes the following steps: S1.1: Disperse porous starch in 40% ethanol solution at a solid-liquid ratio of 1 g: (20-30) mL, add quaternary ammonium cellulose, and stir and disperse thoroughly to obtain a mixed solution; S1.2: Add 0.1 mol / L sodium hydroxide solution to the mixed solution to adjust the pH to 9.5-10.5, then add epichlorohydrin, and heat and stir at 30-40°C for 2-3 hours, then add 0.1 mol / L hydrochloric acid solution to adjust the pH to neutral, centrifuge, wash and freeze-dry to obtain modified porous starch; S1.3: After activation, Bacillus subtilis, Bacillus natto and Rhodococcus gordonii YKSW-6 are suspended in phosphate buffer respectively to prepare Bacillus subtilis suspension, Bacillus natto suspension and Rhodococcus gordonii YKSW-6 suspension with OD600nm of 1.0, and then fully and evenly mix them in equal volume ratio to obtain a mixed bacterial suspension; S1.4: Add the modified porous starch mentioned above to the mixed bacterial suspension at a solid-liquid ratio of 1g: (40-50)mL, shake and react at 160-180r / min for 1-2h, and obtain a composite deodorizing material by centrifugal separation, washing and low-temperature drying.

[0010] Furthermore, S2 specifically includes the following steps: S2.1: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate into deionized water according to the solid-liquid ratio of (2.8 - 3) g : 1 g : (80 - 90) mL, stir well to dissolve, then add cetyltrimethylammonium bromide, stir well and mix, and then add ammonia water to adjust the pH to 10 - 10.5 to obtain a suspension; S2.2: Dissolve zinc nitrate hexahydrate in deionized water according to the solid-liquid ratio of 1 g : (18 - 22) mL to prepare a zinc nitrate solution, and then dropwise add the zinc nitrate solution into the above suspension while stirring. After the addition is completed, continue to stir for 30 - 40 min to obtain a mixed precursor solution; S2.3: Add ammonia water to the above mixed precursor solution to adjust the pH to 10 - 10.5, then transfer it to a hydrothermal reaction kettle, heat and react at 130 - 140 °C for 12 - 14 h, and naturally cool to room temperature to obtain a composite suspension; S2.4: After centrifugally filtering the above composite suspension, wash it with deionized water by centrifugation until the pH is neutral, dry it at a constant temperature of 60 - 80 °C for 8 - 10 h, and then place it in a muffle furnace and calcine it at 500 - 600 °C for 2 - 3 h to obtain a composite carrier material.

[0011] Furthermore, S3 specifically includes the following steps: S3.1: Add the composite essential oil to the composite carrier material prepared in step S2.4 with the same mass, mix well, place it under vacuum adsorption at 0.1 MPa for 1 - 2 h, and after centrifugal separation, remove the excess composite plant essential oil to obtain an essential oil composite material; S3.2: Add the above essential oil composite material to a 5% aqueous solution of sodium dodecyl sulfate according to the solid-liquid ratio of 1 g : (3 - 5) mL, heat and stir evenly at 30 - 40 °C, then add a 3% aqueous solution of sodium alginate and a 3% chitosan solution, and continue to stir for 1 - 2 h to obtain a microcapsule solution; S3.3: Add a 2% aqueous solution of glutaraldehyde to the above microcapsule solution according to the volume ratio of 1 : (6 - 8), let it stand and crosslink for 20 - 24 h, and then obtain composite essential oil microcapsules after freeze-drying and grinding.

[0012] Furthermore, the mass ratio of quaternized cellulose to porous starch is 1 : (4 - 5), and the volume ratio of epichlorohydrin to the mixed solution is 1 : (40 - 50).

[0013] Furthermore, the mass ratio of cetyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1 : (4.5 - 5.5), and the volume ratio of the zinc nitrate solution to the suspension is 1 : (3 - 4).

[0014] Furthermore, the composite essential oil is mixed and compounded from 4 - 6 parts by mass of lemon essential oil, 6 - 8 parts by mass of lavender essential oil, 2 - 3 parts by mass of eucalyptus essential oil, 3 - 5 parts by mass of atractylodes lancea essential oil, and 1 - 3 parts by mass of melaleuca alternifolia essential oil.

[0015] Further, the volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium dodecyl sulfate aqueous solution is (3.5 - 4.5):(1 - 3):1, and the chitosan solution is prepared by dissolving chitosan in a 1% acetic acid solution.

[0016] Further, by mass percentage, the deodorant comprises the following components: 15 - 25% of a composite deodorant material, 10 - 20% of composite essential oil microcapsules, 1 - 3% of a surfactant, 0.03 - 0.05% of benzalkonium bromide, and the balance is water; wherein, the surfactant is glycerol monostearate.

[0017] Further, a deodorant for air disinfection and deodorization is prepared by the preparation process of a deodorant for air disinfection and deodorization described in any one of the above.

[0018] Compared with the prior art, the present invention has at least the following beneficial effects: 1. In the present invention, by first mixing and dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate, and adding cetyltrimethylammonium bromide and ammonia water to prepare a mesoporous nano-hydroxyapatite precursor suspension, and then adding a zinc nitrate solution, carrying out a hydrothermal reaction and calcining to prepare a mesoporous nano-hydroxyapatite-nano-zinc oxide composite carrier material, when the composite essential oil is loaded onto the composite carrier material by the vacuum impregnation method, not only can the composite essential oil have a slow-release effect and improve the long-term deodorization effect of the deodorant, but also because the nano-zinc oxide particles are compounded with the mesoporous nano-hydroxyapatite, the specific surface area of the mesoporous nano-hydroxyapatite can be effectively increased, providing more adsorption sites for the composite essential oil, thereby significantly improving the loading rate of the composite carrier material for the composite essential oil, and further improving the deodorization effect of the deodorant.

[0019] 2. In the present invention, after dispersing the porous starch in an ethanol solution, quaternized cellulose and epichlorohydrin are added for reaction. Through the ring-opening of epichlorohydrin under alkaline conditions, reacting with the hydroxyl groups of the porous starch and the amino groups of the quaternized cellulose to form a cross-linked network, modifying the porous starch, and connecting the quaternized cellulose to the surface of the porous starch. Since the modification of the quaternized cellulose can make the surface of the porous starch rich in positive charges, connecting with the deodorizing microorganisms showing negative charges through ionic bonds, thereby achieving the effect of significantly improving the loading rate of the porous starch for the deodorizing microorganisms, which is beneficial to further improving the deodorization effect of the deodorant.

[0020] 3. In the present invention, the composite essential oil is composed of lemon essential oil, lavender essential oil, eucalyptus essential oil, atractylodes lancea essential oil and melaleuca alternifolia essential oil. Its core components can destroy the bacterial biofilm and target and remove odor molecules, thereby achieving the effect of air disinfection and deodorization. Among them, when the atractylodes lancea essential oil and the melaleuca alternifolia essential oil are used in combination, they can synergistically promote the air deodorization effect of the deodorant in the poultry house. Brief Description of the Drawings

[0021] The accompanying drawings incorporated herein and constituting a part of the specification illustrate embodiments of the present disclosure, and together with the specification are further used to explain the principles of the present disclosure and enable those skilled in the relevant art to implement and use the present disclosure.

[0022] Figure 1 It is a cumulative release rate curve graph of the essential oil composite material and the composite essential oil prepared in Example 1 of the present invention.

[0023] Figure 2 It is a scanning electron microscope image of the composite deodorant material prepared in Comparative Example 2 of the present invention.

[0024] Figure 3 It is a scanning electron microscope image of the composite deodorant material prepared in Example 1 of the present invention.

[0025] Figure 4 It is a scanning electron microscope image of the composite carrier material prepared in Example 1 of the present invention. Detailed Description of the Invention

[0026] The following describes in detail a deodorant for air disinfection and deodorization and its preparation process provided by the present invention in conjunction with the accompanying drawings and specific embodiments.

[0027] Example 1 A preparation process of a deodorant for air disinfection and deodorization, comprising the following steps: S1: Dispersing porous starch in a 40% ethanol solution according to a solid-liquid ratio of 1 g: 20 mL, adding quaternized cellulose, and fully stirring and dispersing to obtain a mixed solution. Then, adding a 0.1 mol / L sodium hydroxide solution to adjust the pH to 9.5, adding epichlorohydrin, heating and stirring the reaction at 30 °C for 2 h, adding a 0.1 mol / L hydrochloric acid solution to adjust the pH to neutral, centrifuging, washing, and freeze-drying to obtain modified porous starch for standby. Among them, the mass ratio of quaternized cellulose to porous starch is 1:4, and the volume ratio of epichlorohydrin to the mixed solution is 1:40. Subsequently, Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6 are activated and then respectively suspended in a phosphate buffer solution to prepare a Bacillus subtilis suspension, a Bacillus natto suspension, and a Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.0. Then, they are fully and uniformly mixed according to an equal volume ratio to obtain a mixed bacterial suspension. Then, adding the modified porous starch to the mixed bacterial suspension according to a solid-liquid ratio of 1 g: 40 mL, oscillating and reacting at 160 r / min for 1 h, centrifuging, washing, and drying at low temperature to obtain a composite deodorant material, and its scanning electron microscope image is as Figure 3 shown; The activation media for the above-mentioned Bacillus subtilis and Bacillus natto include the following components: 15 g of peptone, 2 g of bee pollen, 2 g of yeast extract, 5 g of glucose, 5 g of maltose, 0.1 g of calcium chloride, 0.1 g of magnesium sulfate, 2 g of urea, 5 g of sodium chloride, 2 g of sodium nitrite, 0.008 g of ferrous sulfate, 1 g of dipotassium hydrogen phosphate, and 100 g of distilled water; the activation media for Gordonia rubropertincta YKSW-6 include the following components: 10 g of glucose, 10 g of peptone, 5 g of beef extract, 5 g of sodium chloride, 1.5 g of dipotassium hydrogen phosphate, 0.5 g of potassium dihydrogen phosphate, 0.2 g of magnesium sulfate heptahydrate, 0.01 g of calcium chloride, and 100 g of distilled water; S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water according to the solid-liquid ratio of 2.8 g: 1 g: 80 mL, stir well to dissolve, then add cetyltrimethylammonium bromide, stir well and mix, then add ammonia water to adjust the pH to 10 to obtain a suspension. Among them, the mass ratio of cetyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:4.5. Then dissolve zinc nitrate hexahydrate in deionized water according to the solid-liquid ratio of 1 g: 18 mL to prepare a zinc nitrate solution, and while stirring, drop the zinc nitrate solution into the suspension. After the dropping is completed, continue to stir for 30 min to obtain a mixed precursor solution. Among them, the volume ratio of the zinc nitrate solution to the suspension is 1:3. Subsequently, add ammonia water to the mixed precursor solution to adjust the pH to 10, then transfer it to a hydrothermal reaction kettle, heat and react at 130 °C for 12 h, naturally cool to room temperature, and obtain a composite suspension. Finally, after centrifugally filtering the composite suspension, wash it with deionized water by centrifugation until the pH is neutral, dry it at a constant temperature of 60 °C for 8 h, then place it in a muffle furnace and calcine it at 500 °C for 2 h to obtain a composite carrier material, and its SEM image is as Figure 4 shown; S3: Add the composite essential oil to the composite carrier material prepared in step S2 with the same mass, mix well, place it under vacuum adsorption at 0.1 MPa for 1 h, and after centrifugal separation to remove the excess composite plant essential oil, obtain an essential oil composite material. Among them, the composite essential oil is prepared by mixing and compounding 4 parts by mass of lemon essential oil, 6 parts by mass of lavender essential oil, 2 parts by mass of eucalyptus essential oil, 3 parts by mass of atractylodes lancea essential oil, and 1 part by mass of melaleuca alternifolia essential oil. Then add a 5% sodium dodecyl sulfate aqueous solution to the essential oil composite material according to the solid-liquid ratio of 1 g: 3 mL, heat and stir evenly at 30 °C, then add a 3% sodium alginate aqueous solution and a 3% chitosan solution, and continue to stir for 1 h to obtain a microcapsule solution. Among them, the volume ratio of the chitosan solution, the sodium alginate aqueous solution to the sodium dodecyl sulfate aqueous solution is 3.5: 1: 1, and the chitosan solution is prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, add a 2% glutaraldehyde aqueous solution to the microcapsule solution according to the volume ratio of 1: 6, let it stand and crosslink for 20 h, and then obtain the composite essential oil microcapsules after freeze-drying and grinding; S4: Mix the above-mentioned composite deodorant material, the above-mentioned composite essential oil microcapsules, surfactant, benzalkonium bromide and water, and ultrasonically disperse them for 1 hour to obtain a deodorant, wherein the deodorant includes the following components in mass percentage: 15% composite deodorant material, 10% composite essential oil microcapsules, 1% surfactant, 0.03% benzalkonium bromide, and the balance is water; wherein the surfactant is monoglyceride of fatty acid.

[0028] Embodiment 2 A process for preparing a deodorant for air disinfection and deodorization comprises the following steps: S1: The porous starch was dispersed in a 40% ethanol solution at a solid-liquid ratio of 1g:25mL, and the quaternized cellulose was added and fully stirred and dispersed to obtain a mixed solution. Then, 0.1mol / L sodium hydroxide solution was added to the mixed solution to adjust the pH to 10, and then epichlorohydrin was added, and the mixture was heated and stirred at 35°C for 2.5h, and then 0.1mol / L hydrochloric acid solution was added to adjust the pH to neutral. After centrifugation, washing and freeze-drying, the modified porous starch was obtained for standby use, wherein the mass ratio of the quaternized cellulose to the porous starch was 1:4.5, and the mass ratio of the epichlorohydrin to the mixed solution was 1:4.5. The volume ratio is 1:45, and then Bacillus subtilis, Bacillus natto and Rhodococcus gordonii YKSW-6 are activated and suspended in phosphate buffer respectively to prepare Bacillus subtilis suspension, Bacillus natto suspension and Rhodococcus gordonii YKSW-6 suspension with OD600nm of 1.0, and then fully and evenly mixed in equal volume ratio to obtain a mixed bacterial suspension, and then the modified porous starch is added to the mixed bacterial suspension at a solid-liquid ratio of 1g:45mL, and the reaction is shaken at 170r / min for 1.5h, and the composite deodorant material is obtained by centrifugal separation, washing and low-temperature drying; The activation medium of the above-mentioned Bacillus subtilis and Bacillus natto comprises the following components: 15g of peptone, 2g of bee pollen, 2g of yeast extract, 5g of glucose, 5g of maltose, 0.1g of calcium chloride, 0.1g of magnesium sulfate, 2g of urea, 5g of sodium chloride, 2g of sodium nitrite, 0.008g of ferrous sulfate, 1g of dipotassium hydrogen phosphate, and 100g of distilled water; the activation medium of Rhodococcus gordonii YKSW-6 comprises the following components: 10g of glucose, 10g of peptone, 5g of beef extract, 5g of sodium chloride, 1.5g of dipotassium hydrogen phosphate, 0.5g of potassium dihydrogen phosphate, 0.2g of magnesium sulfate heptahydrate, 0.01g of calcium chloride, and 100g of distilled water; S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate into deionized water according to the solid-liquid ratio of 2.9 g: 1 g: 85 mL, stir well to dissolve, then add cetyltrimethylammonium bromide, stir well and mix, then add ammonia water to adjust the pH to 10.2 to obtain a suspension. Among them, the mass ratio of cetyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:5. Then dissolve zinc nitrate hexahydrate in deionized water according to the solid-liquid ratio of 1 g: 20 mL to prepare a zinc nitrate solution, and while stirring, dropwise add the zinc nitrate solution into the suspension. After the dropping is completed, continue to stir for 35 min to obtain a mixed precursor solution. Among them, the volume ratio of the zinc nitrate solution to the suspension is 1:3.5. Subsequently, add ammonia water to the mixed precursor solution to adjust the pH to 10.2, then transfer it to a hydrothermal reaction kettle, heat and react at 135 °C for 13 h. After naturally cooling to room temperature, a composite suspension is obtained. Finally, the composite suspension is centrifuged and filtered, centrifugally washed with deionized water until the pH is neutral, dried at a constant temperature of 70 °C for 9 h, and then placed in a muffle furnace and calcined at 550 °C for 2.5 h to obtain a composite carrier material; S3: Add the composite essential oil to the composite carrier material prepared in step S2 with the same mass, mix well, place it under vacuum adsorption at 0.1 MPa for 1.5 h, and after centrifugal separation to remove the excess composite plant essential oil, an essential oil composite material is obtained. Among them, the composite essential oil is mixed and compounded from 5 parts by mass of lemon essential oil, 7 parts by mass of lavender essential oil, 2.5 parts by mass of eucalyptus essential oil, 4 parts by mass of atractylodes lancea essential oil, and 2 parts by mass of melaleuca alternifolia essential oil. Then, according to the solid-liquid ratio of 1 g: 4 mL, add the essential oil composite material to a 5% aqueous solution of sodium dodecyl sulfate, heat and stir evenly at 35 °C, then add a 3% aqueous solution of sodium alginate and a 3% chitosan solution, and continue to stir for 1.5 h to obtain a microcapsule solution. Among them, the volume ratio of the chitosan solution, the aqueous sodium alginate solution to the aqueous sodium dodecyl sulfate solution is 4:2:1, and the chitosan solution is prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, add a 2% aqueous solution of glutaraldehyde to the microcapsule solution according to the volume ratio of 1:7, let it stand and crosslink for 22 h, and then obtain composite essential oil microcapsules after freeze-drying and grinding; S4: Mix the above composite deodorant material, the above composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and ultrasonically disperse for 1.5 h to obtain a deodorant. Among them, by mass percentage, the deodorant includes the following components: 20% composite deodorant material, 15% composite essential oil microcapsules, 2% surfactant, 0.04% benzalkonium bromide, and the balance is water; among them, the surfactant is glycerol monostearate.

[0029] Example 3 A preparation process of a deodorant for air disinfection and deodorization, including the following steps: S1: Disperse porous starch in a 40% ethanol solution at a solid-liquid ratio of 1 g: 30 mL, add quaternized cellulose, and stir well to disperse to obtain a mixed solution. Then, add a 0.1 mol / L sodium hydroxide solution to the mixed solution to adjust the pH to 10.5, add epichlorohydrin, and heat and stir the reaction at 40 °C for 3 h. Then, add a 0.1 mol / L hydrochloric acid solution to adjust the pH to neutral. After centrifugation, washing, and freeze-drying, obtain modified porous starch for standby. Among them, the mass ratio of quaternized cellulose to porous starch is 1:5, and the volume ratio of epichlorohydrin to the mixed solution is 1:50. Subsequently, activate Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6 and suspend them in phosphate buffer respectively to prepare a Bacillus subtilis suspension, a Bacillus natto suspension, and a Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.0. Then, mix them evenly according to an equal volume ratio to obtain a mixed bacterial suspension. Then, add the modified porous starch to the mixed bacterial suspension at a solid-liquid ratio of 1 g: 50 mL, and react with shaking at 180 r / min for 2 h. After centrifugal separation, washing, and low-temperature drying, obtain a composite deodorant material; The activation media for the above-mentioned Bacillus subtilis and Bacillus natto include the following components: 15 g of peptone, 2 g of bee pollen, 2 g of yeast extract, 5 g of glucose, 5 g of maltose, 0.1 g of calcium chloride, 0.1 g of magnesium sulfate, 2 g of urea, 5 g of sodium chloride, 2 g of sodium nitrite, 0.008 g of ferrous sulfate, 1 g of dipotassium hydrogen phosphate, and 100 g of distilled water; The activation media for Rhodococcus gordonii YKSW-6 include the following components: 10 g of glucose, 10 g of peptone, 5 g of beef extract, 5 g of sodium chloride, 1.5 g of dipotassium hydrogen phosphate, 0.5 g of potassium dihydrogen phosphate, 0.2 g of magnesium sulfate heptahydrate, 0.01 g of calcium chloride, and 100 g of distilled water; S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water at a solid-liquid ratio of 3 g: 1 g: 90 mL, stir well to dissolve, add cetyltrimethylammonium bromide, stir well to mix, and then add ammonia water to adjust the pH to 10.5 to obtain a suspension. Among them, the mass ratio of cetyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:5.5. Then, dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1 g: 22 mL to prepare a zinc nitrate solution. While stirring, drop the zinc nitrate solution into the suspension. After the dropping is completed, continue to stir for 40 min to obtain a mixed precursor solution. Among them, the volume ratio of the zinc nitrate solution to the suspension is 1:4. Subsequently, add ammonia water to the mixed precursor solution to adjust the pH to 10.5, transfer it to a hydrothermal reaction kettle, heat and react at 140 °C for 14 h, and naturally cool to room temperature to obtain a composite suspension. Finally, after centrifuging and filtering the composite suspension, wash it with deionized water by centrifugation until the pH is neutral, dry it at a constant temperature of 80 °C for 10 h, and then place it in a muffle furnace and calcine it at 600 °C for 3 h to obtain a composite carrier material; S3: Add the compound essential oil to the compound carrier material prepared in step S2 with the same mass. After fully mixing evenly, place it under vacuum adsorption at 0.1 MPa for 2 h. After centrifugal separation and removing the excess compound plant essential oil, an essential oil composite material is obtained. Among them, the compound essential oil is prepared by mixing and compounding 6 parts by mass of lemon essential oil, 8 parts by mass of lavender essential oil, 3 parts by mass of eucalyptus essential oil, 5 parts by mass of atractylodes lancea essential oil, and 3 parts by mass of melaleuca alternifolia essential oil. Then, according to the solid-liquid ratio of 1 g:5 mL, add it to a 5% sodium dodecyl sulfate aqueous solution. After heating and stirring evenly at 40 °C, add a 3% sodium alginate aqueous solution and a 3% chitosan solution, and continue stirring for 2 h to obtain a microcapsule solution. Among them, the volume ratio of the chitosan solution, sodium alginate aqueous solution, and sodium dodecyl sulfate aqueous solution is 4.5:3:1, and the chitosan solution is prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, add a 2% glutaraldehyde aqueous solution to the microcapsule solution according to a volume ratio of 1:8, let it stand for cross-linking for 24 h, and then obtain the compound essential oil microcapsules through freeze-drying and grinding; S4: Mix the above compound deodorant material, the above compound essential oil microcapsules, a surfactant, benzalkonium bromide, and water, and perform ultrasonic dispersion for 2 h to obtain a deodorant. Among them, by mass percentage, the deodorant includes the following components: 25% compound deodorant material, 20% compound essential oil microcapsules, 3% surfactant, 0.05% benzalkonium bromide, and the balance is water; among them, the surfactant is glycerol monostearate.

[0030] Comparative Example 1 The difference between this Comparative Example 1 and Example 1 is that the zinc nitrate solution in step S2 is removed to prepare mesoporous nano-hydroxyapatite, and the compound carrier material in step S3 is replaced with an equal amount of mesoporous nano-hydroxyapatite.

[0031] Comparative Example 2 The difference between this Comparative Example 2 and Example 1 is that the step of modifying the porous starch in step S1 is removed, and the modified porous starch in step S1 is replaced with an equal amount of porous starch, that is, directly add the porous starch to the mixed bacterial suspension for loading. The SEM image of the compound deodorant material obtained after loading is as Figure 2 shown.

[0032] Comparative Example 3 The difference between this Comparative Example 3 and Example 1 is that the atractylodes lancea essential oil in step S3 is replaced with an equal amount of melaleuca alternifolia essential oil.

[0033] Comparative Example 4 The difference between this Comparative Example 4 and Example 1 is that the melaleuca alternifolia essential oil in step S3 is replaced with an equal amount of atractylodes lancea essential oil.

[0034] Test Example Test 1: Respectively put the compound essential oil and the essential oil composite material prepared in Example 1 into dialysis bags, measure the concentration of the essential oil dialyzed out of the dialysis bags at different times, calculate and draw the cumulative release rate curve, and the results are as Figure 1as shown

[0035] From Figure 1 It can be seen that the essential oil composite material has an obvious slow-release effect.

[0036] Test 2: Respectively measure the initial mass of the composite essential oil in step S3 of Examples 1-3 and Comparative Example 1 and record it as m0, and then measure the mass of the excess composite plant essential oil after vacuum adsorption and centrifugal separation and record it as m1. The calculation formula for the loading rate of the composite essential oil is as follows: Loading rate (%) = (m0 - m1) / m0 × 100%. Each group was tested in parallel three times, and the average value was taken. The results are shown in Table 1.

[0037] Table 1: Loading rate of composite essential oil

[0038] As shown in Table 1, the loading rate of the mesoporous nano-hydroxyapatite not compounded with nano-zinc oxide in Comparative Example 1 for the composite essential oil is much lower than that in Example 1. Thus, it can be seen that by first mixing and dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate, adding cetyltrimethylammonium bromide and ammonia water to prepare a suspension of the mesoporous nano-hydroxyapatite precursor, and then adding a zinc nitrate solution, followed by hydrothermal reaction and calcination to prepare a mesoporous nano-hydroxyapatite-nano-zinc oxide composite carrier material, when the composite essential oil is loaded onto the composite carrier material by the vacuum impregnation method, it can provide more adsorption sites for the composite essential oil, thereby significantly improving the loading rate of the composite carrier material for the composite essential oil, and further improving the deodorizing effect of the deodorant.

[0039] Test 3: Respectively take 2 g of the modified porous starch and unmodified porous starch prepared in Examples 1-3 and add them to 100 mL of deionized water for suspension. After ultrasonic dispersion for 30 min, slowly draw 1 mL with a syringe and inject it into the measuring cell of the Zeta potential analyzer. Turn on the Zeta potential analyzer to measure the Zate potential. The results are shown in Table 2.

[0040] Table 2: Zate potential measurement results of modified porous starch and unmodified porous starch

[0041] As shown in Table 2, after modifying the porous starch with quaternized cellulose, it can make the surface of the porous starch rich in positive charges, and connect with the deodorizing microorganisms with negative charges through ionic bonds, thereby achieving the effect of significantly improving the loading rate of the porous starch for the deodorizing microorganisms, which is beneficial to further improving the deodorizing effect of the deodorant.

[0042] In addition, from Figure 2 and Figure 3It can be seen that compared with unmodified porous starch, more microorganisms are distributed in the pores of the modified porous starch, indicating that the modification with quaternized cellulose can effectively improve the loading rate of porous starch for microorganisms.

[0043] Test 4: Detection of hydrogen sulfide removal effect: Place the detection instrument in a 5L airtight glass container with a lid, then introduce hydrogen sulfide into the glass container until the concentration of hydrogen sulfide in the bottle is about 300 mg / L. Then, spray 120 g of the deodorants prepared in Examples 1-3 and Comparative Examples 3-4 into the container respectively, and detect the hydrogen sulfide removal rate after 2 h. The detection method for the ammonia removal effect is the same as that for the hydrogen sulfide removal effect, and the detection results are shown in Table 3.

[0044] Table 3: Detection results of hydrogen sulfide and ammonia removal effects

[0045] As can be seen from Table 3, after replacing atractylodes essential oil with melaleuca alternifolia essential oil or replacing melaleuca alternifolia essential oil with atractylodes essential oil in Comparative Example 3 and Comparative Example 4, the deodorants prepared have lower removal effects on hydrogen sulfide and ammonia than those in Example 1. Thus, it can be seen that the combined use of atractylodes essential oil and melaleuca alternifolia essential oil can synergistically promote the air deodorization effect of the deodorant on poultry houses.

[0046] The above embodiments merely illustrate the principles and effects of the present invention, rather than limiting the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A preparation process of a deodorant for air disinfection and deodorization, characterized in that, It includes the following steps: S1: Modify porous starch with quaternized cellulose, and then use the modified porous starch to load Bacillus subtilis, Bacillus natto and Rhodococcus gordoniae YKSW-6 to obtain a composite deodorant material; S2: Dissolve calcium nitrate tetrahydrate and diammonium hydrogen phosphate in deionized water, then add cetyltrimethylammonium bromide and zinc nitrate solution, mix well, carry out hydrothermal reaction, and after calcination, obtain a composite carrier material; S3: Use the above composite carrier material to load the composite essential oil, then add it to an aqueous solution of sodium dodecyl sulfate, stir and mix evenly, add an aqueous solution of sodium alginate and a chitosan solution, continue to stir and mix, and add an aqueous solution of glutaraldehyde for cross-linking to obtain composite essential oil microcapsules; S4: Mix the above composite deodorant material, the above composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and disperse them ultrasonically for 1-2 h to obtain a deodorant.

2. The preparation process of a deodorant for air disinfection and deodorization according to claim 1, characterized in that, S1 specifically includes the following steps: S1.1: Disperse porous starch in a 40% ethanol solution according to a solid-liquid ratio of 1 g:(20-30) mL, add quaternized cellulose, and stir and disperse well to obtain a mixed solution; S1.2: Add a 0.1 mol / L sodium hydroxide solution to the above mixed solution to adjust the pH to 9.5-10.5, then add epichlorohydrin, heat and stir at 30-40 °C for 2-3 h, then add a 0.1 mol / L hydrochloric acid solution to adjust the pH to neutral, and after centrifugation, washing and freeze-drying, obtain modified porous starch; S1.3: After activating Bacillus subtilis, Bacillus natto and Rhodococcus gordoniae YKSW-6, suspend them in phosphate buffer respectively to prepare a Bacillus subtilis suspension, a Bacillus natto suspension and a Rhodococcus gordoniae YKSW-6 suspension with an OD600nm of 1.0, and then mix them evenly according to an equal volume ratio to obtain a mixed bacterial suspension; S1.4: Add the above modified porous starch to the mixed bacterial suspension according to a solid-liquid ratio of 1 g:(40-50) mL, shake and react at 160-180 r / min for 1-2 h, and after centrifugal separation, washing and low-temperature drying, obtain a composite deodorant material.

3. The preparation process of a deodorant for air disinfection and deodorization according to claim 2, characterized in that, S2 specifically includes the following steps: S2.1: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water according to a solid-liquid ratio of (2.8-3) g:1 g:(80-90) mL, stir and dissolve well, then add cetyltrimethylammonium bromide, stir and mix well, and then add ammonia water to adjust the pH to 10-10.5 to obtain a suspension; S2.2: Dissolve zinc nitrate hexahydrate in deionized water according to a solid-liquid ratio of 1 g:(18-22) mL to prepare a zinc nitrate solution, and then dropwise add the zinc nitrate solution to the above suspension while stirring. After the addition is completed, continue to stir for 30-40 min to obtain a mixed precursor solution; S2.3: Add ammonia water to the above mixed precursor solution to adjust the pH to 10-10.5, then transfer it to a hydrothermal reaction kettle, heat and react at 130-140 °C for 12-14 h, and naturally cool to room temperature to obtain a composite suspension; S2.4: After centrifugation and filtration, the composite suspension is washed with deionized water until the pH is neutral, dried at a constant temperature of 60-80°C for 8-10h, and then placed in a muffle furnace and calcined at 500-600°C for 2-3h to obtain a composite carrier material.

4. The preparation process of a deodorant for air disinfection and deodorization according to claim 3, characterized in that, S3 specifically includes the following steps: S3.1: adding the composite essential oil to the composite carrier material obtained in step S2.4 of equal mass, mixing them thoroughly and evenly, placing them under vacuum adsorption at 0.1 MPa for 1-2 hours, and removing excess composite plant essential oil by centrifugation to obtain an essential oil composite material; S3.2: Add the essential oil composite material to a 5% sodium dodecyl sulfate aqueous solution at a solid-liquid ratio of 1 g: (3-5) mL, heat and stir at 30-40 °C, then add a 3% sodium alginate aqueous solution and a 3% chitosan solution, and continue stirring for 1-2 hours to obtain a microcapsule solution; S3.3: Add 2% glutaraldehyde aqueous solution to the above microcapsule solution in a volume ratio of 1: (6-8), let it stand for cross-linking for 20-24 hours, and then freeze-dry and grind to obtain composite essential oil microcapsules.

5. The preparation process of a deodorant for air disinfection and deodorization according to claim 2, characterized in that, The mass ratio of quaternized cellulose to porous starch is 1:(4-5), and the volume ratio of epichlorohydrin to the mixed solution is 1:(40-50).

6. The preparation process of a deodorant for air disinfection and deodorization according to claim 3, characterized in that, The mass ratio of hexadecyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:(4.5-5.5), and the volume ratio of zinc nitrate solution to suspension is 1:(3-4).

7. The preparation process of a deodorant for air disinfection and deodorization according to claim 4, characterized in that, The composite essential oil is prepared by mixing and compounding 4-6 parts by weight of lemon essential oil, 6-8 parts by weight of lavender essential oil, 2-3 parts by weight of eucalyptus essential oil, 3-5 parts by weight of atractylodes essential oil and 1-3 parts by weight of melaleuca alternifolia essential oil.

8. The preparation process of a deodorant for air disinfection and deodorization according to claim 4, characterized in that, The volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium dodecyl sulfate aqueous solution is (3.5-4.5):(1-3):1, and the chitosan solution is prepared by dissolving chitosan in a 1% acetic acid solution.

9. The preparation process of a deodorant for air disinfection and deodorization according to claim 1, characterized in that, The deodorant comprises the following components in percentage by mass: 15-25% of a composite deodorizing material, 10-20% of a composite essential oil microcapsule, 1-3% of a surfactant, 0.03-0.05% of benzalkonium bromide, and the remainder is water; wherein the surfactant is monoglyceride of fatty acid.

10. A deodorant for air disinfection and deodorization, characterized in that, The deodorant is prepared by the preparation process of a deodorant for air disinfection and deodorization as described in any one of claims 1 to 9.

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