Preparation method of transparent shell-based acaricidal sterilization and disinfection solution

Abstract

The application discloses a preparation method of a transparent shell-based mite-removing sterilization and disinfection liquid, which comprises the following steps: (1) cleaning a shell with a brush, soaking the shell in a NaOH solution, washing the shell with clean water until neutral, and drying the shell; (2) placing the material obtained in the step (1) in a muffle furnace for calcination, crushing the material after cooling, adding a certain volume of pure water into a sealed container, stirring and hydrating, and obtaining calcined shell powder; (3) stirring the calcined shell powder for 2-3 hours, dispersing the calcined shell powder in pure water, removing large particles through centrifugation, and passing the solution through an ultrafiltration membrane to obtain a clear membrane-passed solution; and (4) adding a carboxymethyl chitosan solution into the clear membrane-passed solution, introducing CO2, and fully stirring and reacting at room temperature to obtain the transparent shell-based mite-removing sterilization and disinfection liquid. The transparent shell-based mite-removing sterilization and disinfection liquid prepared by taking a shell as a main body has the effects of sterilization and bacteriostasis, is safe, clear, transparent and stable, has excellent mite-removing effect, and is a natural disinfectant.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of marine waste resource development and utilization, and particularly relates to a preparation method of a transparent shell-based mite-removing sterilization and disinfection solution. BACKGROUND

[0002] Shell is a kind of natural resource, and at present, the utilization of shell is limited to edible parts, and the shell part accounting for more than 60% of the mass of shellfish is rarely processed and utilized, and is discarded in a landfill or filled in the sea, and a large amount of stacking occupies a lot of land resources, and causes environmental pollution. Shell is basically composed of calcium carbonate crystals accounting for 95% of the weight of shell and organic matter accounting for about 5% of the weight of shell, and in recent years, shell is widely applied in the fields of medicine, preservation and preservation, artificial bone material, drug carrier, sewage treatment, bionic material and the like. After high-temperature calcination, shell forms powder with alkaline properties such as Ca(OH)2 and CaO, and can be used as a kind of natural sterilization material, which is non-toxic, non-irritating, safe, mild and effective.

[0003] CN111466412A discloses a shell-based disinfectant and deodorant and a preparation method thereof, which comprises the following steps: permeating treatment of shell by using a surfactant to obtain permeated shell; microwave puffing treatment of the permeated shell to obtain puffing-treated shell; crushing treatment of the puffing-treated shell to obtain crushed shell; dissolving the crushed shell in water to obtain a calcium shell-based suspension solution; centrifugal treatment of the calcium shell-based suspension solution to remove the precipitate to obtain the shell-based disinfectant and deodorant. The disinfectant and deodorant can kill bacteria and eliminate odor well, but the preparation method is complicated, and white powder is easily left on articles and corners which are not easy to clean when the disinfectant and deodorant are applied, and the application scene is very limited. CN107232235A discloses a micro-nano shell water disinfectant and a preparation method thereof. The main raw material of the disinfectant is micro-nano shell powder after calcination and hydration. The preparation method of the micro-nano shell powder comprises the following steps: a cleaning step, an acid pickling step, a drying step, a calcination and crushing step and a nanometerization step. The technical scheme adopts natural shell powder as the main raw material, and can effectively remove harmful bacteria in ponds and the like after optimization, but the effect of the technical scheme on sterilization of Escherichia coli is mainly studied, and the sterilization effect of the product on other bacteria is unknown.

[0004] It should be emphasized that the biggest bottleneck of shell powder as a sterilization and disinfection agent is that the water solubility is poor, and the powder is easy to leave white. So far, many kinds of shell-based disinfectants or decontaminants can only exist in the form of powder or suspension liquid with poor stability, and the disinfection function is also single. SUMMARY

[0005] The application aims to overcome the defects of the prior art, and provides a preparation method of a transparent shell-based mite-removing sterilization and disinfection solution.

[0006] The disinfection principle of the present application is that the shell is dissolved in the carboxymethyl chitosan solution after calcination, and after CO2 is introduced, Ca 2+ reacts with CO3 2- to generate nano calcium carbonate. Under the induction of macromolecular template effect, the nano-porous microcrystalline calcium carbonate with special sharp structure is formed, which is more likely to adsorb bacteria. Since the solution is alkaline, microorganisms are very sensitive to the change of pH value of their living medium. The excessively high pH value can weaken the survival ability of microorganisms to some extent, thereby destroying the structure of bacterial cells and playing a role in sterilization and acarid removal.

[0007] The technical solution of the present application is as follows:

[0008] A preparation method of a transparent shell-based acarid removal and sterilization disinfectant solution, comprising the following steps:

[0009] (1) clean the shell with a brush, soak it in a 4-6% NaOH solution, then rinse it with clean water until it is neutral, and dry it;

[0010] (2) place the material obtained in step (1) in a muffle furnace for calcination at 800-1100°C for 3-4h, crush it after cooling, and then add pure water to the closed container, stir and hydrate, and grind to obtain calcined shell powder with a particle size of 400-1000;

[0011] (3) disperse the calcined shell powder in pure water at a concentration of 2-3g / L, stir for 2-3h, remove the large particles by centrifugation, and pass the solution through an ultrafiltration membrane at 24-26°C to obtain a clear membrane-passed solution;

[0012] (4) after adding a carboxymethyl chitosan solution with a concentration of 9-11g / L to the clear membrane-passed solution, introduce CO2, and stir at room temperature to fully react, so that Ca 2+ reacts with CO3 2- to generate nano-porous microcrystalline calcium carbonate with special sharp structure under the action of macromolecular template, thereby obtaining the transparent shell-based acarid removal and sterilization disinfectant solution.

[0013] In a preferred embodiment of the present application, the raw material of the shell is derived from at least one of oysters, mussels, clams and scallops.

[0014] In a preferred embodiment of the present application, in step (2), the mass ratio of the material obtained in step (1) to pure water is 1:35-45.

[0015] Further preferably, in step (2), the mass ratio of the material obtained in step (1) to pure water is 2.8-3.2:1.

[0016] In a preferred embodiment of the present application, the molecular weight cut-off of the ultrafiltration membrane is 200-400 kDa.

[0017] Further preferably, the model of the ultrafiltration membrane is UF200 or UF400.

[0018] Further preferably, the transmembrane pressure of the ultrafiltration membrane is 0.2-0.4 MPa.

[0019] Further preferably, the transmembrane pressure of the ultrafiltration membrane is 0.3 MPa.

[0020] In a preferred embodiment of the present application, in the step (4), the volume ratio of the clarified permeate liquid to the carboxymethyl chitosan solution is 4-6:1.

[0021] Further preferably, in the step (4), the ratio of the clarified permeate liquid to CO2 is 100 mL:0.5-1 L.

[0022] The present application has the following beneficial effects:

[0023] 1. The transparent shell-based acaricidal sterilization and disinfection liquid prepared by the present application has not only bactericidal and bacteriostatic effects, but also safety, clarity, transparency, stability, and excellent acaricidal effect, and is a natural disinfectant.

[0024] 2. The transparent shell-based acaricidal sterilization and disinfection liquid prepared by the present application is clear and transparent, and has good stability. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The electron microscope image of the nanoporous microcrystalline calcium carbonate in the transparent shell-based acaricidal sterilization and disinfection liquid prepared in Example 1 of the present application.

[0026] Figure 2 The bactericidal effect photos of the transparent shell-based acaricidal sterilization and disinfection liquid prepared in Example 1 of the present application on Escherichia coli and Staphylococcus aureus.

[0027] Figure 3 The bactericidal performance test result graph of the transparent shell-based acaricidal sterilization and disinfection liquid prepared in Example 1 of the present application on Escherichia coli 8099, Staphylococcus aureus ATCC 6538, Pseudomonas aeruginosa ATCC 15442, and Candida albicans ATCC 10231.

[0028] Figure 4 The bactericidal performance test result graph of the transparent shell-based acaricidal sterilization and disinfection liquid prepared in Example 1 of the present application on human coronavirus 229E. DETAILED DESCRIPTION

[0029] The technical solutions of the present application are further described and explained in the following specific embodiments combined with the drawings.

[0030] Example 1

[0031] The shells were cleaned in an ultrasonic cleaning machine for 20 min after being brushed several times with a brush to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water several times until neutral, and dried in an oven for 3 h. 50 g of the shells were calcined in a muffle furnace at 900°C for 3 h, cooled, crushed, and then stirred with 16 g of pure water in a sealed container to hydrate, and ground to obtain 800-mesh calcined shell powder. 0.25 g of the calcined shell powder was added to 100 mL of pure water and stirred for 2 h, and large particles were removed by centrifugation. The solution was filtered at 25°C using a pressure of 0.2 MPa, a membrane filtration device, and an ultrafiltration membrane UF200 to obtain a clear filtrate. 20 mL of a 10 g / L carboxymethyl chitosan solution was added to the clear filtrate, 1 L of CO2 was introduced, and the solution was stirred for 2 h to obtain a transparent shell-based acaricidal sterilization and disinfection solution with a shell powder particle size of 1.5 μm (as shown in FIG. 1). Figure 1 The transparent shell-based acaricidal sterilization and disinfection solution obtained was clear and transparent, and had a sterilization rate of >99.9999% for E. coli, >99.9999% for Staphylococcus aureus, >99.9999% for Pseudomonas aeruginosa, >99.999% for Candida albicans, >99.99% for human coronavirus 229E, and 100% for mites.

[0032] Example 2

[0033] The shells were cleaned in an ultrasonic cleaning machine for 20 min after being brushed several times with a brush to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water several times until neutral, and dried in an oven for 3 h and then knocked into small pieces. 50 g of the shells were calcined in a muffle furnace at 1000°C for 4 h, cooled, crushed, and then stirred with 16 g of pure water in a sealed container to hydrate, and ground to obtain 600-mesh calcined shell powder. 0.28 g of the calcined shell powder was added to 100 mL of pure water and stirred for 2 h, and large particles were removed by centrifugation. The solution was filtered at 25°C using a pressure of 0.4 MPa, a membrane filtration device, and an ultrafiltration membrane UF400 to obtain a clear filtrate. 20 mL of a 10 g / L carboxymethyl chitosan solution was added to the clear filtrate, 1 L of CO2 was introduced, and the solution was stirred for 2 h to obtain a transparent shell-based acaricidal sterilization and disinfection solution with a shell powder particle size of 2 μm. The transparent shell-based acaricidal sterilization and disinfection solution obtained was clear and transparent, and had a sterilization rate of >99.9999% for E. coli, >99.9999% for Staphylococcus aureus, >99.9999% for Pseudomonas aeruginosa, >99.999% for Candida albicans, and 100% for mites.

[0034] Example 3

[0035] The shells are cleaned in an ultrasonic cleaning machine after being brushed several times with a brush for 20 min to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water until neutral, dried in an oven for 3 h, then broken into small pieces; 50 g of the shells are calcined in a muffle furnace at 1000°C for 3 h, cooled, crushed, then added to a sealed container with 16 g of pure water to hydrate, obtaining 400 mesh calcined shell powder; 0.3 g of the calcined shell powder is added to 100 mL of pure water to stir for 3 h, centrifuged to remove large particles, and filtered at 25°C using a pressure of 0.3 MPa, a membrane equipment and an ultrafiltration membrane UF200, obtaining a clear membrane liquid. 20 mL of 10 g / L carboxymethyl chitosan solution is added to the clear membrane liquid, 0.5 L of CO2 is introduced, and the mixture is stirred for 2 h to obtain a transparent shell-based acaricidal sterilization and disinfection solution with a shell powder particle size of 1.5 μm. The prepared transparent shell-based acaricidal sterilization and disinfection solution is clear and transparent, and the sterilization rate of Escherichia coli is >99.9999%, the sterilization rate of Staphylococcus aureus is >99.9999%, the sterilization rate of Pseudomonas aeruginosa is >99.9999%, the sterilization rate of Candida albicans is >99.999%, and the acaricidal rate is 100%.

[0036] Example 4:

[0037] The shells are cleaned in an ultrasonic cleaning machine after being brushed several times with a brush for 20 min to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water until neutral, dried in an oven for 3 h, then broken into small pieces; 50 g of the shells are calcined in a muffle furnace at 1000°C for 3 h, cooled, crushed, then added to a sealed container with 16 g of pure water to hydrate, obtaining 400 mesh calcined shell powder; 0.3 g of the calcined shell powder is added to 100 mL of pure water to stir for 3 h, centrifuged to remove large particles, and filtered at 25°C using a pressure of 0.3 MPa, a membrane equipment and an ultrafiltration membrane UF200, obtaining a clear membrane liquid. 20 mL of 10 g / L carboxymethyl chitosan solution is added to the clear membrane liquid, 0.5 L of CO2 is introduced, and the mixture is stirred for 2 h to obtain a transparent shell-based acaricidal sterilization and disinfection solution with a shell powder particle size of 1.5 μm. The prepared transparent shell-based acaricidal sterilization and disinfection solution is clear and transparent, and the sterilization rate of Escherichia coli is >99.9999%, the sterilization rate of Staphylococcus aureus is >99.9999%, the sterilization rate of Pseudomonas aeruginosa is >99.9999%, the sterilization rate of Candida albicans is >99.999%, and the acaricidal rate is 100%.

[0038] Comparative Example 1:

[0039] The shell is cleaned in an ultrasonic cleaning machine for 20 min after being brushed several times with a brush to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water until neutral, dried in an oven for 3 h, and then broken into small pieces; 50 g of the shell is calcined in a muffle furnace at 500°C for 3 h, cooled, crushed, and then stirred with 16 g of pure water in a sealed container to obtain 800 mesh calcined shell powder; 0.25 g of the calcined shell powder is stirred in 100 mL of pure water for 2 h, centrifuged to remove large particles, and then filtered at 25°C using a pressure of 0.4 MPa, a membrane filtration device, and ultrafiltration membrane UF200 to obtain a clear filtrate. 20 mL of 10 g / L carboxymethyl chitosan solution is added to the clear filtrate, 0.5 L of CO2 is introduced, and the mixture is stirred for 2 h to obtain a contrast disinfectant 1 with a shell powder particle size of 1.5 μm. The prepared contrast disinfectant 1 is clear and transparent, and has a sterilization rate of 50.1% for E. coli, 30.2% for Staphylococcus aureus, 27.5% for Pseudomonas aeruginosa, 14.2% for Candida albicans, and a mite killing rate of 30%.

[0040] Comparative Example 2

[0041] The shell is cleaned in an ultrasonic cleaning machine for 20 min after being brushed several times with a brush to remove surface impurities, then soaked in 5% NaOH solution for 3 h, washed with clean water until neutral, dried in an oven for 3 h, and then broken into small pieces; 50 g of the shell is calcined in a muffle furnace at 500°C for 3 h, cooled, crushed, and then stirred with 16 g of pure water in a sealed container to obtain 800 mesh calcined shell powder; 0.25 g of the calcined shell powder is stirred in 100 mL of pure water for 2 h, centrifuged to remove large particles, and then filtered at 25°C using a pressure of 0.4 MPa, a membrane filtration device, and ultrafiltration membrane UF200 to obtain a clear filtrate. 20 mL of 10 g / L carboxymethyl chitosan solution is added to the clear filtrate, 0.5 L of CO2 is introduced, and the mixture is stirred for 2 h to obtain a contrast disinfectant 1 with a shell powder particle size of 1.5 μm. The prepared contrast disinfectant 1 is clear and transparent, and has a sterilization rate of 50.1% for E. coli, 30.2% for Staphylococcus aureus, 27.5% for Pseudomonas aeruginosa, 14.2% for Candida albicans, and a mite killing rate of 30%.

[0042] Comparative Example 3

[0043] The shell is cleaned in an ultrasonic cleaning machine after being brushed with a brush for multiple times, and the ultrasonic time is 20 min, surface impurities are removed, then the shell is soaked in 5% NaOH solution for 3 h, then washed with clean water for multiple times until neutral, dried in an oven for 3 h, then knocked into small pieces; 50 g of the shell is calcined in a muffle furnace at 1000 ℃ for 4 h, cooled, then crushed, added with 16 g of pure water in a sealed container for hydration, and 400 mesh calcined shell powder is obtained; 0.3 g of the calcined shell powder is added into 100 mL of pure water for stirring for 2 h, large particles are removed by centrifugation, 20 mL of 10 g / L carboxymethyl chitosan solution is added, 0.5 L of CO2 is introduced, and the reaction is fully stirred for 2 h, and then a comparison disinfectant 3 is obtained. The prepared comparison disinfectant 3 is relatively turbid, has a little white precipitate, the sterilization rate on escherichia coli is > 60.6%, the sterilization rate on staphylococcus aureus is > 52.7%, the sterilization rate on pseudomonas aeruginosa is > 63.8%, the sterilization rate on candida albicans is > 67.9%, and the mite killing rate is 70%.

[0044] The shell is cleaned in an ultrasonic cleaning machine after being brushed with a brush for multiple times, and the ultrasonic time is 20 min, surface impurities are removed, then the shell is soaked in 5% NaOH solution for 3 h, then washed with clean water for multiple times until neutral, dried in an oven for 3 h, then knocked into small pieces; 50 g of the shell is calcined in a muffle furnace at 1000 ℃ for 4 h, cooled, then crushed, added with 16 g of pure water in a sealed container for hydration, and 400 mesh calcined shell powder is obtained; 0.3 g of the calcined shell powder is added into 100 mL of pure water for stirring for 2 h, large particles are removed by centrifugation, 20 mL of 10 g / L carboxymethyl chitosan solution is added, 0.5 L of CO2 is introduced, and the reaction is fully stirred for 2 h, and then a comparison disinfectant 3 is obtained. The prepared comparison disinfectant 3 is relatively turbid, has a little white precipitate, the sterilization rate on escherichia coli is > 60.6%, the sterilization rate on staphylococcus aureus is > 52.7%, the sterilization rate on pseudomonas aeruginosa is > 63.8%, the sterilization rate on candida albicans is > 67.9%, and the mite killing rate is 70%.

[0045] The mite killing effect test of the transparent shell-based mite killing and sterilization disinfectant solution of the present application is as follows:

[0046] Test method: The test is carried out according to the verification method of GB / T 24253--2009 Evaluation of Anti-mite Performance of Textiles and Disinfection Technical Specification (2002 Edition) Ministry of Health (Health Law Supervision and Issue (2002) No. 282), and the mite removal of the transparent shell-based mite killing and sterilization disinfectant solution of the present application is investigated, and the mite killing effect of the transparent shell-based mite killing and sterilization disinfectant solution prepared in Example 1 is shown in Table 1.

[0047] The transparent shell-based acarid-removing sterilization and disinfection solution prepared in Example 1 has a mite removal rate of 100% compared with the control group, which proves that the disinfection solution has excellent acarid-removing effect.

[0048] Table 1 Test results of the transparent shell-based acarid-removing sterilization and disinfection solution prepared in Example 1 of the present application.

[0049]

[0050] Note:

[0051] 1. Sample mite killing rate = (number of dead mites (average)) / (number of initial mites (average)) x 100%

[0052] 2. The results are for reference only.

[0053] 3. The mite number for experiment: TV033.

[0054] The test report is only for the purpose of customer scientific research, teaching, internal quality control, product research and development, and is only for internal reference.

[0055] Bactericidal performance test of the transparent shell-based acarid-removing sterilization and disinfection solution of the present application:

[0056] The transparent shell-based acarid-removing sterilization and disinfection solution of the present application has good bactericidal performance, and the test is carried out according to 2.1.1.7.4 of the Bacterium Quantitative Killing Test of the Technical Specifications for Disinfection of the Ministry of Public Health of the People's Republic of China, and the bactericidal rates of Escherichia coli 8099, Staphylococcus aureus ATCC 6538, Pseudomonas aeruginosa ATCC 15442 and Candida albicans ATCC 10231 can all reach more than 99.999%. Figure 3 Test results of the transparent shell-based acarid-removing sterilization and disinfection solution prepared in Example 1 of the present application on the bactericidal performance of the above four bacteria.

[0057] The bactericidal effect of the transparent shell-based acarid-removing sterilization and disinfection solution prepared in Example 1 is shown in Figure 2 Fig. 1, wherein the left graph is an Escherichia coli plate after treatment with the transparent shell-based acarid-removing sterilization and disinfection solution, and the right graph is a Staphylococcus aureus plate after treatment with the transparent shell-based acarid-removing sterilization and disinfection solution, and the sterile growth in the graph proves that the disinfection solution has a high killing effect on bacteria.

[0058] Stability accelerated test of the transparent shell-based acarid-removing sterilization and disinfection solution of the present application:

[0059] The test refers to 7.1.1 of GB / T 38499-2020 "Method for evaluating stability of disinfectant", and observes and records whether the disinfectant has color change, whether precipitate or suspended matter is produced, and investigates the stability of the transparent shell-based acarid-killing and sterilizing disinfectant solution of the application. The stability comparison results of the transparent shell-based acarid-killing and sterilizing disinfectant solutions prepared in Examples 1-4 and the comparative disinfectant solutions 1-5 prepared in Comparative Examples 1-5 are shown in Table 2. Under the environmental condition of 54℃ for 14 days, the transparent shell-based acarid-killing and sterilizing disinfectant solution of the application still maintains clear and transparent, and has good stability.

[0060] Table 3 Stability comparison results of the transparent shell-based acarid-killing and sterilizing disinfectant solutions prepared in Examples 1-4 of the application and the comparative disinfectant solutions 1-4 prepared in Comparative Examples 1-5

[0061]

[0062]

[0063] In addition, the transparent shell-based acarid-killing and sterilizing disinfectant solution of the application can achieve a sterilization rate of 99.99% for human coronavirus 229E ATCC VR-740. Figure 4 Test results of the sterilization performance of the transparent shell-based acarid-killing and sterilizing disinfectant solution prepared in Example 1 of the application on human coronavirus 229E.

[0064] The above is only the preferred embodiment of the application, and therefore cannot limit the scope of the application. Equivalent changes and modifications made according to the scope and content of the application should still be within the scope of the application.

Claims

1. A method for preparing a transparent shell-based mite-killing and sterilizing disinfectant, characterized by: The steps include: (1) Soak the clean shells in 4-6% NaOH solution, then rinse with clean water until neutral and dry; (2) The material obtained in step (1) is placed in a muffle furnace and calcined at 800-1100°C for 3-4 hours, crushed after cooling, and then transferred to a sealed container, stirred with pure water for hydration, and ground to obtain calcined shell powder of 400-1000 mesh; (3) The calcined shell powder is dispersed in pure water at a concentration of 2-3 g / L by stirring for 2-3 hours, and after centrifugation to remove large particles, it is passed through an ultrafiltration membrane with a molecular weight cutoff of 200-400 kDa at 24-26°C to obtain a clarified membrane solution; (4) After adding 9-11 g / L carboxymethyl chitosan solution to the clarified membrane solution, introduce CO2 and stir at room temperature to fully react to make Ca 2+ With CO3 2- Nanoporous microcrystalline calcium carbonate with a special spike-like structure is generated under the action of the macromolecular template, thereby obtaining the transparent shell-based mite removal and sterilization disinfectant.

2. The preparation method according to claim 1, wherein: The shell material is at least one of oysters, mussels, clams and scallops.

3. The preparation method according to claim 1, wherein: In the step (2), the mass ratio of the material obtained in the step (1) to pure water is 2.8-3.2:

1.

4. The preparation method according to claim 1, wherein: The model of the ultrafiltration membrane is UF200 or UF400.

5. The preparation method according to claim 1, wherein: The transmembrane pressure of the ultrafiltration membrane is 0.2-0.4 MPa.

6. The preparation method according to claim 5, wherein: The transmembrane pressure of the ultrafiltration membrane is 0.3 MPa.

7. The preparation method according to claim 1, wherein: In the step (4), the volume ratio of the clarified membrane liquid to the carboxymethyl chitosan solution is 4-6:

1.

8. The preparation method according to claim 7, wherein: In the step (4), the ratio of the clarified membrane liquid to CO2 is 100mL:0.5-1L.

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