Deodorant for air disinfection and deodorization and preparation process thereof

Abstract

The present invention provides a deodorant for air disinfection and deodorization and a preparation process thereof, belonging to the field of air purification technology; the deodorant comprises the following components: a composite deodorizing material, composite essential oil microcapsules, a surfactant, benzalkonium bromide, and water. The present invention comprises the following components: calcium nitrate tetrahydrate and diammonium hydrogen phosphate are first mixed and dissolved, and cetyltrimethylammonium bromide and ammonia water are added to prepare a mesoporous nano-hydroxyapatite precursor suspension, and then a zinc nitrate solution is added, followed by a hydrothermal reaction and calcination to prepare a composite carrier material. When the composite essential oil is loaded into the composite carrier material by a vacuum impregnation method, not only can the composite essential oil have a sustained-release effect, thereby improving the long-lasting deodorizing effect of the deodorant, but also more adsorption sites can be provided for the composite essential oil, thereby significantly increasing the loading rate of the composite carrier material for the composite essential oil, thereby improving the deodorizing effect of the deodorant.

Description

Technical Field

[0001] The present 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 replenished frequently; chemical deodorants use chemical reagents to react with odor molecules to achieve the purpose of deodorization. Its characteristics are rapid reaction but short-term 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 and 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 in plant essential oils, such as polyphenols, terpenes, and aldehydes, can undergo oxidation-reduction, acid-base neutralization, addition condensation and other reactions with odor molecules, changing the molecular structure of odor 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 quickly fail, and the disinfection and deodorization effect 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, converting them into harmless substances through biochemical reactions, and can also degrade skatole, thereby reducing irritation to the respiratory tract and conjunctiva of poultry and livestock, and reducing the incidence and mortality of diseases. Moreover, compared with free microorganisms, fixing microorganisms in a carrier 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 shortcomings of 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:

[0009] S1: Porous starch was modified with quaternized cellulose, and then Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6 were loaded on the modified porous starch to obtain a composite deodorizing material;

[0010] S2: dissolving nitric acid tetrahydrate and diammonium hydrogen phosphate in deionized water, adding cetyltrimethylammonium bromide and zinc nitrate solution, mixing thoroughly, performing a hydrothermal reaction, and calcining to obtain a composite support material;

[0011] S3: using the composite carrier material to load the composite essential oil, adding it to a sodium lauryl sulfate aqueous solution, stirring and mixing it 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 composite essential oil microcapsules;

[0012] S4: mixing the composite deodorizing material, the composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and performing ultrasonic dispersion for 1-2 hours to obtain a deodorant.

[0013] Furthermore, S1 specifically includes the following steps:

[0014] S1.1: Disperse porous starch in 40% ethanol solution at a solid-liquid ratio of 1 g:(20-30) mL, add quaternized cellulose, and stir thoroughly to obtain a mixed solution.

[0015] S1.2: Add 0.1 mol / L sodium hydroxide solution to the above 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.

[0016] S1.3: Activate Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6, respectively, and suspend them in phosphate buffer to prepare Bacillus subtilis suspension, Bacillus natto suspension, and Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.0. The suspensions are then thoroughly and evenly mixed in equal volumes to obtain a mixed bacterial suspension.

[0017] S1.4: Add the modified porous starch to the mixed bacterial suspension at a solid-liquid ratio of 1 g: (40-50) mL, shake at 160-180 rpm for 1-2 hours, and obtain a composite deodorizing material by centrifugation, washing, and low-temperature drying.

[0018] Furthermore, S2 specifically includes the following steps:

[0019] S2.1: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water at a solid-liquid ratio of (2.8-3) g:1 g:(80-90) mL and stir thoroughly to dissolve. Then add cetyltrimethylammonium bromide and stir thoroughly to mix. Then, add aqueous ammonia to adjust the pH to 10-10.5 to obtain a suspension.

[0020] S2.2: Dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1 g:(18-22) mL to prepare a zinc nitrate solution. Add the zinc nitrate solution dropwise to the suspension while stirring. Continue stirring for 30-40 minutes to obtain a mixed precursor solution.

[0021] S2.3: Add ammonia water to the above mixed precursor solution to adjust the pH to 10-10.5, then transfer to a hydrothermal reactor, heat at 130-140°C for 12-14 hours, and naturally cool to room temperature to obtain a composite suspension;

[0022] 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 8-10 hours, and then placed in a muffle furnace and calcined at 500-600°C for 2-3 hours to obtain a composite support material.

[0023] Furthermore, S3 specifically includes the following steps:

[0024] S3.1: Add the composite essential oil to an equal amount of the composite carrier material prepared in step S2.4, mix thoroughly, and place under vacuum at 0.1 MPa for 1-2 hours. Centrifuge to remove excess composite plant essential oil to obtain an essential oil composite material.

[0025] S3.2: Add the essential oil composite material to a 5% sodium lauryl 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;

[0026] 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.

[0027] 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).

[0028] Furthermore, 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).

[0029] Furthermore, the composite essential oil is prepared by mixing 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 essential oil and 1-3 parts by mass of Melaleuca alternifolia essential oil.

[0030] Furthermore, the volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium lauryl 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.

[0031] Furthermore, the deodorant includes the following components, calculated by mass percentage: 15-25% of a composite deodorizing material, 10-20% of composite essential oil microcapsules, 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.

[0032] Furthermore, a deodorant for air disinfection and deodorization is prepared by any of the above-mentioned preparation processes for a deodorant for air disinfection and deodorization.

[0033] Compared with the prior art, the present invention has at least the following beneficial effects:

[0034] 1. In the present invention, calcium nitrate tetrahydrate and diammonium hydrogen phosphate are first mixed and dissolved, and cetyltrimethylammonium bromide and ammonia water are added to prepare a mesoporous nano-hydroxyapatite precursor suspension, and then a zinc nitrate solution is added, 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 into the composite carrier material by a vacuum impregnation method, not only can the composite essential oil have a sustained-release effect, thereby improving the long-lasting deodorizing effect of the deodorant, but also because the nano-zinc oxide particles composite mesoporous nano-hydroxyapatite can effectively increase the specific surface area of the mesoporous nano-hydroxyapatite, 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, thereby improving the deodorizing effect of the deodorant.

[0035] 2. In the present invention, after the porous starch is dispersed in an ethanol solution, quaternized cellulose and epichlorohydrin are added to react. The epichlorohydrin is ring-opened under alkaline conditions and reacts with the hydroxyl groups of the porous starch and the amino groups of the quaternized cellulose to form a cross-linked network. The porous starch is modified so that the quaternized cellulose is connected to the surface of the porous starch. Due to the modification of the quaternized cellulose, abundant positive charges are distributed on the surface of the porous starch, which can be connected to the negatively charged deodorizing microorganisms through ionic bonds, thereby significantly improving the loading rate of the porous starch on the deodorizing microorganisms, which is conducive to further improving the deodorizing effect of the deodorant.

[0036] 3. In the present invention, the composite essential oil is compounded by lemon essential oil, lavender essential oil, eucalyptus essential oil, atractylodes essential oil and Melaleuca alternifolia essential oil. The core components thereof can destroy bacterial biofilms and target the removal of odor molecules, thereby achieving the effect of disinfecting and deodorizing the air. Among them, when atractylodes essential oil and Melaleuca alternifolia essential oil are used in combination, they can synergistically promote the deodorizing effect of the deodorant on the air in the poultry house. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable one skilled in the relevant art to make and use the present disclosure.

[0038] Figure 1 This is a graph showing the cumulative release rate of the essential oil composite material and the composite essential oil prepared in Example 1 of the present invention.

[0039] Figure 2 This is a scanning electron microscope image of the composite deodorizing material prepared in Comparative Example 2 of the present invention.

[0040] Figure 3 This is a scanning electron microscope image of the composite deodorizing material prepared in Example 1 of the present invention.

[0041] Figure 4 This is a scanning electron microscope image of the composite carrier material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0042] 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.

[0043] Example 1 A process for preparing a deodorant for air disinfection and deodorization comprises the following steps:

[0044] S1: The porous starch was dispersed in a 40% ethanol solution at a solid-liquid ratio of 1 g: 20 mL, quaternized cellulose was added, and the mixture was fully stirred and dispersed to obtain a mixed solution, and then 0.1 mol / L sodium hydroxide solution was added to the mixed solution to adjust the pH to 9.5, and then epichlorohydrin was added, and the mixture was heated and stirred at 30 ° C for 2 h, and then 0.1 mol / 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 quaternized cellulose to porous starch was 1:4, and the volume ratio of epichlorohydrin to the mixed solution was 1:40, then Bacillus subtilis, Bacillus natto and Rhodococcus gordonii YKSW-6 were 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 modified porous starch was added to the mixed bacterial suspension at a solid-liquid ratio of 1g:40mL, and the reaction was shaken at 160r / min for 1h. After centrifugation, washing and low-temperature drying, a composite deodorizing material was obtained, and its electron microscope scanning image is shown as follows Figure 3 As shown;

[0045] The activation medium for the Bacillus subtilis and Bacillus natto comprises the following components: 15 g peptone, 2 g bee pollen, 2 g yeast extract, 5 g glucose, 5 g maltose, 0.1 g calcium chloride, 0.1 g magnesium sulfate, 2 g urea, 5 g sodium chloride, 2 g sodium nitrite, 0.008 g ferrous sulfate, 1 g dipotassium hydrogen phosphate, and 100 g distilled water; the activation medium for Rhodococcus gordonii YKSW-6 comprises the following components: 10 g glucose, 10 g peptone, 5 g beef extract, 5 g sodium chloride, 1.5 g dipotassium hydrogen phosphate, 0.5 g potassium dihydrogen phosphate, 0.2 g magnesium sulfate heptahydrate, 0.01 g calcium chloride, and 100 g distilled water;

[0046] S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water at a solid-liquid ratio of 2.8g:1g:80mL, stir and dissolve thoroughly, then add hexadecyltrimethylammonium bromide, stir and mix thoroughly, then add ammonia water to adjust the pH to 10 to obtain a suspension, wherein the mass ratio of hexadecyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:4.5, then dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1g:18mL to prepare a zinc nitrate solution, then add the zinc nitrate solution dropwise to the suspension while stirring, and the addition is complete. After that, stirring was continued for 30 minutes to obtain a mixed precursor solution, wherein the volume ratio of zinc nitrate solution to suspension solution was 1:3, and then ammonia water was added to the mixed precursor solution to adjust the pH to 10, and then transferred to a hydrothermal reactor, heated at 130 ° C for 12 hours, and naturally cooled to room temperature to obtain a composite suspension. Finally, the composite suspension was centrifuged and filtered, and then washed with deionized water until the pH was neutral, and dried at a constant temperature of 60 ° C for 8 hours, and then placed in a muffle furnace and calcined at 500 ° C for 2 hours to obtain a composite carrier material, as shown in the electron microscope scanning image. Figure 4 As shown;

[0047] S3: Add the composite essential oil to the composite carrier material prepared in step S2 of equal mass, mix thoroughly, place under vacuum adsorption at 0.1 MPa for 1 hour, centrifuge and remove excess composite plant essential oil to obtain an essential oil composite material, wherein the composite essential oil is a mixture of 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 essential oil and 1 part by mass of Melaleuca alternifolia essential oil, and then add 5% sodium lauryl sulfate to the essential oil composite material at a solid-liquid ratio of 1g:3mL. The aqueous solution was heated at 30° C. and stirred uniformly, and then a 3% sodium alginate aqueous solution and a 3% chitosan solution were added, and the stirring was continued for 1 hour to obtain a microcapsule solution, wherein the volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium lauryl sulfate aqueous solution was 3.5:1:1, and the chitosan solution was prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, a 2% glutaraldehyde aqueous solution was added to the microcapsule solution at a volume ratio of 1:6, and after standing and cross-linking for 20 hours, the composite essential oil microcapsules were obtained by freeze-drying and grinding.

[0048] S4: Mix the above-mentioned composite deodorizing material, the above-mentioned composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and ultrasonically disperse them for 1 hour to obtain a deodorant, wherein the deodorant includes the following components, by mass percentage: 15% composite deodorizing 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.

[0049] Example 2 A process for preparing a deodorant for air disinfection and deodorization comprises the following steps:

[0050] S1: The porous starch was dispersed in a 40% ethanol solution at a solid-liquid ratio of 1g:25mL, quaternized cellulose was added, and the mixture was fully stirred and dispersed to obtain a mixed solution, and 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 quaternized cellulose to porous starch was 1:4.5, and the mass ratio of 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 to prepare Bacillus subtilis suspension, Bacillus natto suspension and Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.0, and then fully and uniformly mixed in an equal volume ratio to obtain a mixed bacterial suspension, and then 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 deodorizing material is obtained through centrifugation, washing and low-temperature drying.

[0051] The activation medium for the Bacillus subtilis and Bacillus natto comprises the following components: 15 g peptone, 2 g bee pollen, 2 g yeast extract, 5 g glucose, 5 g maltose, 0.1 g calcium chloride, 0.1 g magnesium sulfate, 2 g urea, 5 g sodium chloride, 2 g sodium nitrite, 0.008 g ferrous sulfate, 1 g dipotassium hydrogen phosphate, and 100 g distilled water; the activation medium for Rhodococcus gordonii YKSW-6 comprises the following components: 10 g glucose, 10 g peptone, 5 g beef extract, 5 g sodium chloride, 1.5 g dipotassium hydrogen phosphate, 0.5 g potassium dihydrogen phosphate, 0.2 g magnesium sulfate heptahydrate, 0.01 g calcium chloride, and 100 g distilled water;

[0052] S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water at a solid-liquid ratio of 2.9g:1g:85mL, stir and dissolve thoroughly, then add hexadecyltrimethylammonium bromide, stir and mix thoroughly, then add ammonia water to adjust the pH to 10.2 to obtain a suspension, wherein the mass ratio of hexadecyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:5, then dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1g:20mL to prepare a zinc nitrate solution, then add the zinc nitrate solution dropwise to the suspension while stirring, and complete the addition. After the mixture is completed, stirring is continued for 35 minutes to obtain a mixed precursor solution, wherein the volume ratio of the zinc nitrate solution to the suspension solution is 1:3.5, and then ammonia water is added to the mixed precursor solution to adjust the pH to 10.2, and then transferred to a hydrothermal reactor, heated at 135°C for 13 hours, and naturally cooled to room temperature to obtain a composite suspension. Finally, the composite suspension is centrifuged and filtered, and then centrifuged and washed with deionized water until the pH is neutral, and dried at a constant temperature of 70°C for 9 hours, and then placed in a muffle furnace and calcined at 550°C for 2.5 hours to obtain a composite support material;

[0053] S3: Add the composite essential oil to the composite carrier material prepared in step S2 of equal mass, mix thoroughly, place under 0.1MPa for vacuum adsorption for 1.5h, centrifuge and remove excess composite plant essential oil to obtain an essential oil composite material, wherein the composite essential oil is prepared by mixing 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 essential oil and 2 parts by mass of Melaleuca alternifolia essential oil, and then add 5% dodecyl sulfide to the essential oil composite material at a solid-liquid ratio of 1g:4mL. The mixture was heated at 35° C. and stirred evenly, and then a 3% sodium alginate aqueous solution and a 3% chitosan solution were added, and the stirring was continued for 1.5 hours to obtain a microcapsule solution, wherein the volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium lauryl sulfate aqueous solution was 4:2:1, and the chitosan solution was prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, a 2% glutaraldehyde aqueous solution was added to the microcapsule solution at a volume ratio of 1:7, and after standing and cross-linking for 22 hours, the composite essential oil microcapsules were obtained by freeze-drying and grinding.

[0054] S4: Mix the above-mentioned composite deodorizing material, the above-mentioned composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and ultrasonically disperse them for 1.5 hours to obtain a deodorant, wherein the deodorant includes the following components, by mass percentage: 20% composite deodorizing material, 15% composite essential oil microcapsules, 2% surfactant, 0.04% benzalkonium bromide, and the balance is water; wherein the surfactant is monoglyceride of fatty acid.

[0055] Example 3 A process for preparing a deodorant for air disinfection and deodorization comprises the following steps:

[0056] S1: The porous starch was dispersed in a 40% ethanol solution at a solid-liquid ratio of 1g:30mL, quaternized cellulose was added, and the mixture was fully stirred and dispersed to obtain a mixed solution, and then 0.1mol / L sodium hydroxide solution was added to the mixed solution to adjust the pH to 10.5, and then epichlorohydrin was added, and the mixture was heated and stirred at 40°C for 3h, and then 0.1mol / L hydrochloric acid solution was added to adjust the pH to neutral, and the modified porous starch was obtained by centrifugation, washing and freeze-drying for standby use, wherein the mass ratio of quaternized cellulose to porous starch was 1:5, and the mass ratio of epichlorohydrin to the mixed solution was 1:5. The volume ratio is 1:50, and then Bacillus subtilis, Bacillus natto and Rhodococcus gordonii YKSW-6 are activated and suspended in phosphate buffer to prepare Bacillus subtilis suspension, Bacillus natto suspension and Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.0, and then fully and uniformly mixed in an equal volume ratio to obtain a mixed bacterial suspension, and then modified porous starch is added to the mixed bacterial suspension at a solid-liquid ratio of 1g:50mL, and the reaction is shaken at 180r / min for 2h, and the composite deodorizing material is obtained through centrifugation, washing and low-temperature drying.

[0057] The activation medium for the Bacillus subtilis and Bacillus natto comprises the following components: 15 g peptone, 2 g bee pollen, 2 g yeast extract, 5 g glucose, 5 g maltose, 0.1 g calcium chloride, 0.1 g magnesium sulfate, 2 g urea, 5 g sodium chloride, 2 g sodium nitrite, 0.008 g ferrous sulfate, 1 g dipotassium hydrogen phosphate, and 100 g distilled water; the activation medium for Rhodococcus gordonii YKSW-6 comprises the following components: 10 g glucose, 10 g peptone, 5 g beef extract, 5 g sodium chloride, 1.5 g dipotassium hydrogen phosphate, 0.5 g potassium dihydrogen phosphate, 0.2 g magnesium sulfate heptahydrate, 0.01 g calcium chloride, and 100 g distilled water;

[0058] S2: Add calcium nitrate tetrahydrate and diammonium hydrogen phosphate to deionized water at a solid-liquid ratio of 3g:1g:90mL, stir and dissolve thoroughly, then add hexadecyltrimethylammonium bromide, stir and mix thoroughly, then add ammonia water to adjust the pH to 10.5 to obtain a suspension, wherein the mass ratio of hexadecyltrimethylammonium bromide to calcium nitrate tetrahydrate is 1:5.5, then dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1g:22mL to prepare a zinc nitrate solution, then add the zinc nitrate solution dropwise to the suspension while stirring, and add dropwise After completion, stirring was continued for 40 minutes to obtain a mixed precursor solution, wherein the volume ratio of the zinc nitrate solution to the suspension solution was 1:4, and then ammonia water was added to the mixed precursor solution to adjust the pH to 10.5, and then transferred to a hydrothermal reactor, heated at 140°C for 14 hours, and naturally cooled to room temperature to obtain a composite suspension. Finally, the composite suspension was centrifuged and filtered, and then centrifuged and washed with deionized water until the pH was neutral, and dried at a constant temperature of 80°C for 10 hours, and then placed in a muffle furnace and calcined at 600°C for 3 hours to obtain a composite support material;

[0059] S3: Add the composite essential oil to the composite carrier material prepared in step S2 of equal mass, mix thoroughly, place under vacuum adsorption at 0.1 MPa for 2 h, centrifuge and remove excess composite plant essential oil to obtain an essential oil composite material, wherein the composite essential oil is a mixture of 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 essential oil and 3 parts by mass of Melaleuca alternifolia essential oil, and then add 5% sodium lauryl sulfate to the essential oil composite material at a solid-liquid ratio of 1 g: 5 mL. The aqueous solution was heated at 40° C. and stirred uniformly, and then a 3% sodium alginate aqueous solution and a 3% chitosan solution were added, and stirring was continued for 2 hours to obtain a microcapsule solution, wherein the volume ratio of the chitosan solution, the sodium alginate aqueous solution and the sodium lauryl sulfate aqueous solution was 4.5:3:1, and the chitosan solution was prepared by dissolving chitosan in a 1% acetic acid solution. Subsequently, a 2% glutaraldehyde aqueous solution was added to the microcapsule solution at a volume ratio of 1:8, and after standing and cross-linking for 24 hours, the composite essential oil microcapsules were obtained by freeze-drying and grinding.

[0060] S4: Mix the above-mentioned composite deodorizing material, the above-mentioned composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and ultrasonically disperse them for 2 hours to obtain a deodorant, wherein the deodorant includes the following components, by mass percentage: 25% composite deodorizing material, 20% composite essential oil microcapsules, 3% surfactant, 0.05% benzalkonium bromide, and the balance is water; wherein the surfactant is monoglyceride of fatty acid.

[0061] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the zinc nitrate solution in step S2 is removed to prepare mesoporous nano-hydroxyapatite, and the composite carrier material in step S3 is replaced by an equal amount of mesoporous nano-hydroxyapatite.

[0062] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the step of modifying 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, the porous starch is directly added to the mixed bacterial suspension for loading. The electron microscope scanning image of the composite deodorizing material obtained after loading is as follows: Figure 2 shown.

[0063] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the Atractylodes lancea essential oil in step S3 is replaced by an equal amount of Melaleuca alternifolia essential oil.

[0064] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the Melaleuca alternifolia essential oil in step S3 is replaced by an equal amount of Atractylodes lancea essential oil.

[0065] Test Example 1: The composite essential oil and the essential oil composite material prepared in Example 1 were placed in dialysis bags, respectively, and the concentration of essential oil dialyzed out of the composite essential oil in the dialysis bag at different times was measured. The cumulative release rate curve was calculated and plotted. The results are shown in FIG. Figure 1 shown.

[0066] from Figure 1 It can be seen that the essential oil composite material has an obvious sustained-release effect.

[0067] Test 2: The initial mass of the composite essential oil in step S3 of Examples 1-3 and Comparative Example 1 was measured and recorded as m0, and the excess mass of the composite plant essential oil after vacuum adsorption and centrifugal separation was measured and recorded as m1. The loading rate of the composite essential oil was calculated as follows:

[0068] Load rate (%) = (m0-m1) / m0×100%. Each group was tested three times in parallel and the average value was taken. The results are shown in Table 1.

[0069] Table 1: Loading rate of compound essential oils

[0070]

[0071] As shown in Table 1, the loading rate of the mesoporous nano-hydroxyapatite not composited with nano-zinc oxide on the composite essential oil in Comparative Example 1 is much lower than that in Example 1. It can be seen that 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 zinc nitrate solution, carrying out hydrothermal reaction and calcination to prepare a mesoporous nano-hydroxyapatite-nano-zinc oxide composite carrier material, when the composite essential oil is loaded into the composite carrier material by a vacuum impregnation method, more adsorption sites can be provided for the composite essential oil, thereby significantly improving the loading rate of the composite carrier material for the composite essential oil, thereby improving the deodorizing effect of the deodorant.

[0072] Test 3: 2 g of the modified porous starch and unmodified porous starch prepared in Examples 1-3 were respectively added to 100 mL of deionized water and suspended. After ultrasonic dispersion for 30 minutes, 1 mL was slowly drawn out with a syringe and injected into the measuring cell of the Zeta potential meter. The Zeta potential meter was turned on and the Zeta potential was measured. The results are shown in Table 2.

[0073] Table 2: Zate potential measurement results of modified porous starch and unmodified porous starch

[0074]

[0075] As shown in Table 2, after the porous starch is modified with quaternized cellulose, abundant positive charges can be distributed on the surface of the porous starch, which can be connected with the negatively charged deodorizing microorganisms through ionic bonds, thereby significantly improving the loading rate of the porous starch on the deodorizing microorganisms, which is beneficial to further improve the deodorizing effect of the deodorant.

[0076] In addition, from Figure 2 and Figure 3 It can be seen that compared with the unmodified porous starch, more microorganisms are distributed in the pores of the modified porous starch, indicating that the modification of quaternary ammonium cellulose can effectively increase the loading rate of porous starch for microorganisms.

[0077] Test 4:

[0078] Hydrogen sulfide removal effect test: The detection instrument was placed in a 5L sealed glass container with a lid, and then hydrogen sulfide was added to the glass container until the concentration of hydrogen sulfide in the bottle was about 300 mg / L. Then, 120 g of the deodorant prepared in Examples 1-3 and Comparative Examples 3-4 were sprayed into the container, and the hydrogen sulfide removal rate was tested after 2 hours.

[0079] The ammonia removal effect test method is the same as the hydrogen sulfide removal effect test method, and the test results are shown in Table 3.

[0080] Table 3: Hydrogen sulfide and ammonia removal effect test results

[0081]

[0082] As can be seen from Table 3, in Comparative Examples 3 and 4, after replacing the essential oil of Atractylodes lancea with the essential oil of Melaleuca alternifolia or replacing the essential oil of Melaleuca alternifolia with the essential oil of Atractylodes lancea, the removal effect of the deodorant for hydrogen sulfide and ammonia is lower than that in Example 1. It can be seen that the combination of the essential oil of Atractylodes lancea and the essential oil of Melaleuca alternifolia can synergistically promote the deodorization effect of the deodorant on the air in the poultry house.

[0083] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A process for preparing a deodorant for air disinfection and deodorization, characterized in that: The steps include: S1: Porous starch was modified with quaternized cellulose, and then Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6 were loaded on the modified porous starch to obtain a composite deodorizing material; S2: dissolving nitric acid tetrahydrate and diammonium hydrogen phosphate in deionized water, adding cetyltrimethylammonium bromide and zinc nitrate solution, mixing thoroughly, performing a hydrothermal reaction, and calcining to obtain a composite support material; S3: using the composite carrier material to load the composite essential oil, adding it to a sodium lauryl sulfate aqueous solution, stirring and mixing it 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 composite essential oil microcapsules; S4: mixing the composite deodorizing material, the composite essential oil microcapsules, a surfactant, benzalkonium bromide and water, and performing ultrasonic dispersion for 1-2 hours 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 40% ethanol solution at a solid-liquid ratio of 1 g:(20-30) mL, add quaternized cellulose, and stir thoroughly to obtain a mixed solution. S1.2: Add 0.1 mol / L sodium hydroxide solution to the above 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: Activate Bacillus subtilis, Bacillus natto, and Rhodococcus gordonii YKSW-6, respectively, and suspend them in phosphate buffer to prepare Bacillus subtilis suspension, Bacillus natto suspension, and Rhodococcus gordonii YKSW-6 suspension with an OD600nm of 1.

0. The suspensions are then thoroughly and evenly mixed in equal volumes to obtain a mixed bacterial suspension. S1.4: Add the modified porous starch to the mixed bacterial suspension at a solid-liquid ratio of 1 g: (40-50) mL, shake at 160-180 rpm for 1-2 hours, and obtain a composite deodorizing material by centrifugation, washing, and low-temperature drying.

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 at a solid-liquid ratio of (2.8-3) g:1 g:(80-90) mL and stir thoroughly to dissolve. Then add cetyltrimethylammonium bromide and stir thoroughly to mix. Then, add aqueous ammonia to adjust the pH to 10-10.5 to obtain a suspension. S2.2: Dissolve zinc nitrate hexahydrate in deionized water at a solid-liquid ratio of 1 g:(18-22) mL to prepare a zinc nitrate solution. Add the zinc nitrate solution dropwise to the suspension while stirring. Continue stirring for 30-40 minutes 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 to a hydrothermal reactor, heat at 130-140°C for 12-14 hours, 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 8-10 hours, and then placed in a muffle furnace and calcined at 500-600°C for 2-3 hours to obtain a composite support 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: Add the composite essential oil to an equal amount of the composite carrier material prepared in step S2.4, mix thoroughly, and place under vacuum at 0.1 MPa for 1-2 hours. Centrifuge to remove excess composite plant essential oil to obtain an essential oil composite material. S3.2: Add the essential oil composite material to a 5% sodium lauryl 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 process for preparing 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 process for preparing a deodorant for air disinfection and deodorization according to claim 4, characterized in that: The composite essential oil is prepared by mixing 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 process for preparing 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 lauryl 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 process for preparing 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 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 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 according to any one of claims 1 to 9.

Images