Monovalent stable high-concentration peracetic acid compound disinfectant and preparation method thereof

Abstract

The invention discloses a unitary stable high-concentration peracetic acid compound disinfectant and a preparation method thereof. The high-concentration stable peracetic acid compound disinfectant is prepared from the following components in percentage by weight: 10 to 20 percent of peracetic acid, 2 to 10 percent of hydrogen peroxide, 0.05 to 1 percent of corrosion inhibitor, 0.1 to 1 percent of stabilizer and the balance of deionized water, the peracetic acid is obtained by catalyzing acetic acid with the following catalyst: one or two of 1-pentyl-3-methylimidazole phosphotungstate, 1-butyl-3-methylimidazole phosphotungstate and phosphotungstic acid. The peracetic acid in the unitary peracetic acid composite disinfectant is good in stability, the shelf life is two years or more, the disinfection and sterilization effect is good, the peracetic acid is diluted until the peracetic acid content is 500 mg / L and acts for 8 min, the peracetic acid is diluted until the peracetic acid content is 750 mg / L and acts for 6 min, the peracetic acid is diluted until the peracetic acid content is 1000 mg / L and acts for 2 min, 10 < 6 > CFU bacillus subtilis black variant spores on a carrier are completely killed, the sterilization effect is achieved, and the unitary peracetic acid composite disinfectant is simple in process, safe, easy to operate and suitable for industrial production. The catalyst can be recycled and reused, and has economic advantages.

Description

Technical Field

[0001] The invention relates to a mono-stable high-concentration peracetic acid compound disinfectant and a preparation method thereof, belonging to the technical field of disinfection. Background Art

[0002] The molecular formula of peracetic acid is CH3COOOH, and its molecular weight is 76.05. It is a colorless liquid with a pungent odor. It is a strong oxidant and can oxidize compounds such as alkenes, amines, phenols, iodobenzenes, ketones, and adamantane. Peracetic acid has shown good application prospects in the field of disinfection. Compared with traditional chlorine disinfection, it is cleaner and more environmentally friendly. While having broad-spectrum disinfection activity, it almost does not generate toxic disinfection by-products. It has received widespread attention in recent years. A mixed disinfectant with peracetic acid and hydrogen peroxide as the main components has the characteristics of high efficiency, wide sterilization range, non-toxicity, and no secondary pollution. It has been widely used in the disinfection of equipment, tools, pipelines, packaging containers, etc., as well as spraying or heated fumigation for terminal disinfection. However, the existing peracetic acid spray requires 100 mg / m 3 Or heating fumigation at least 1000mg / m 3 The content can effectively disinfect the air.

[0003] As strong oxidizing substances, hydrogen peroxide and peracetic acid cannot be stored stably for a long time. In order to overcome the instability of peracetic acid and hydrogen peroxide, most of the products on the market in recent years are binary packaging, that is, the product is divided into two liquids A and B, which are usually stored in separate bottles. Equal amounts are mixed the day before use, and then diluted to the required concentration after standing for a period of time, which is inconvenient to use.

[0004] Currently, the existing peracetic acid disinfectants on the market generally use concentrated sulfuric acid as a catalyst, which is dangerous during production, transportation and use. On the one hand, the residual concentrated sulfuric acid may continue to catalyze the synthesis of peracetic acid due to environmental changes, or decompose the product and the residual hydrogen peroxide therein, resulting in leakage, explosion and other accidents during transportation or storage of the product; on the other hand, due to the strong corrosiveness of concentrated sulfuric acid, the application of the product in the field of food processing machinery and medical equipment disinfection is limited. The present invention is specially proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a single-unit stable peracetic acid composite disinfectant with economic advantages and safety. The disinfectant has slight corrosion to aluminum and basically no corrosion to stainless steel, has a shelf life of more than two years, and the catalyst can be filtered and recovered for use.

[0006] The high-concentration stable peracetic acid compound disinfectant provided by the present invention is composed of the following components in percentage by weight:

[0007] Peracetic acid 10-20%, hydrogen peroxide 2-10%, corrosion inhibitor 0.05-1%, stabilizer 0.1-1% and the balance deionized water.

[0008] Wherein, the peracetic acid is obtained by catalyzing acetic acid with the following catalyst:

[0009] One or both of 1-pentyl-3-methylimidazolium phosphotungstate and 1-butyl-3-methylimidazolium phosphotungstate;

[0010] In the reaction system, the amount of the catalyst is 0.05%-1% (W / V, g / ml).

[0011] The preparation process of the 1-pentyl-3-methylimidazolium phosphotungstate and the 1-butyl-3-methylimidazolium phosphotungstate is as follows: dissolve phosphotungstic acid in water to prepare a solution; then add 1-butyl-3-methylimidazolium bromide [Bmim] Br (1-pentyl-3-methylimidazolium bromide) to the phosphotungstic acid aqueous solution, which is relatively viscous at the beginning, and the stirring speed needs to be controlled at about 1000 revolutions. During the stirring process, it is necessary to observe and reduce the stirring speed in time within 2 hours to reduce splashing, and stir at room temperature for 8-24 hours to obtain a white precipitate. After filtering and washing with water for more than 3 times until there is no bromide ion in the filtrate, the obtained solid is dried at 60-120°C for 10-24 hours to obtain a white powder catalyst.

[0012] Preferably, the corrosion inhibitor is one or more of laurylamine dipropylene diamine, carboxylic acid type α-iminoacetic acid, quaternary ammonium salt, sodium molybdate, fatty alcohol polyoxyethylene ether, potassium sorbate and sodium silicate.

[0013] Preferably, the stabilizer is one or more of citric acid, hydrolyzed polymaleic anhydride, sodium tripolyphosphate, hydroxyethylethylenediaminetriacetic acid, disodium nitrilotriacetate, ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, sodium glucoheptanoate, polyoxyethylene ether and phosphoric acid.

[0014] Preferably, the quaternary ammonium salt is selected from at least one of the following: a single-chain quaternary ammonium salt and a double-chain quaternary ammonium salt.

[0015] The single-chain quaternary ammonium salt is an alkyl dimethyl benzyl ammonium halide, and its structural formula is shown in Formula I:

[0016]

[0017] In formula I, n=8-18, X=Br - or Cl - ;

[0018] The alkyl dimethyl benzyl ammonium halide may specifically be benzalkonium chloride (n=12), benzalkonium bromide (n=12) or (a mixture of n=8-18 or a single) alkyl dimethyl benzyl ammonium halide.

[0019] The double-chain quaternary ammonium salt is a dialkyl dimethyl ammonium halide, and its structural formula is shown in Formula II:

[0020]

[0021] In formula II, m and n each independently represent an integer of 8 or 10, and X = Br - or Cl - .

[0022] The dialkyldimethylammonium halide may specifically be didecyldimethylammonium chloride, octyl-decyl-dimethylammonium chloride, or dioctyldimethylammonium chloride.

[0023] The quaternary ammonium salt is further preferably a mixture of the alkyl dimethyl benzyl ammonium halide and dialkyl dimethyl ammonium halide in a mass ratio of (5-3): (4-1);

[0024] The quaternary ammonium salt may specifically be a mixture of didecyldimethylammonium chloride and benzalkonium chloride in a mass ratio of 2:3.

[0025] The composite disinfectant of the present invention is made of the following components in percentage by mass:

[0026]

[0027] Preferably:

[0028]

[0029] The preparation method of the composite disinfectant of the present invention comprises the following steps: mixing hydrogen peroxide, acetic acid and a catalyst, stirring at 37°C to 40°C for 6-24h, then adding a stabilizer and a corrosion inhibitor and stirring evenly, and filtering to remove the catalyst to obtain the composite disinfectant.

[0030] The compound disinfectant of the present invention can be used as a sterilizing agent for:

[0031] 1) Used for high-level disinfection and sterilization of heat-labile medical devices;

[0032] 2) Used for high-level disinfection and sterilization in high-level biosafety laboratories, high-risk infectious disease foci, and biosafety incident sites to kill bacterial spores, viruses, bacterial propagules, and fungi in the air and on the surface of objects, and achieve a sterilization effect.

[0033] It is specifically used in the form of liquid immersion, spraying, atomization and gas fumigation.

[0034] Wherein, the bacterial spores are selected from at least one of the following: Bacillus anthracis spores, Bacillus subtilis var. niger spores, Bacillus stearothermophilus spores, and Bacillus cereus spores;

[0035] The virus comprises an enveloped virus and a non-enveloped virus, and is selected from at least one of the following: polio virus, HIV, mad cow virus, Creutzfeldt-Jakob virus, new coronavirus, hand, foot and mouth disease virus, avian influenza virus, influenza A (H1N1) virus and influenza A (H7N9) virus;

[0036] The bacteria and fungi are selected from at least one of the following: intestinal pathogens, pyogenic cocci, pathogenic yeasts, common pathogens of hospital infections and drug-resistant bacteria.

[0037] The monovalent peracetic acid composite disinfectant provided by the present invention has good stability, a shelf life of more than two years, and good disinfection and sterilization effects. The peracetic acid content is diluted to 500 mg / L and acts for 8 minutes, 750 mg / L and acts for 6 minutes, and 1000 mg / L and acts for 2 minutes. 6 The CFU black variant of Bacillus subtilis spores are completely killed to achieve a sterilization effect. In addition, the process of the invention is simple, safe, and easy to operate, and the catalyst can be recovered and reused, which has an economic advantage. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The present invention is a flow chart for preparing the mono-stable composite peracetic acid disinfectant. DETAILED DESCRIPTION

[0039] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, biological materials, etc. used in the following examples are all commercially available unless otherwise specified.

[0040] Example 1: Monovalent stable composite peracetic acid disinfectant

[0041] The disinfectant is prepared from the following components: Take the preparation of 1000mL of disinfectant as an example.

[0042]

[0043] Preparation: First, prepare the stabilizer 1-butyl-3-methylimidazolium phosphotungstate. The preparation process is as follows: dissolve phosphotungstic acid (0.01mol, 28.8g) in 100ml water to make a solution. Then add 1-butyl-3-methylimidazolium bromide [Bmim]Br (0.06mol, 13.2g) to the phosphotungstic acid aqueous solution, control the stirring speed to about 1000 rpm, and observe and reduce the stirring speed in time within 2 hours during the stirring process to reduce splashing. Stir at room temperature for 12 hours to obtain a white precipitate. After filtering and washing with water for more than 3 times until there is no bromide ion in the filtrate, the obtained solid is dried at 80℃ for 24 hours to obtain a white powder [Bmim]3PW 12 O 40 catalyst.

[0044]

[0045] Preparation process of the composite disinfectant of this embodiment: 333mL hydrogen peroxide (30%), 666mL glacial acetic acid and 0.05g 1-butyl-3-methylimidazole phosphotungstate are placed in a 2000mL three-necked flask and stirred magnetically for 10h. Transfer to a glass bottle and let stand for 15d. Filter out the catalyst, add 3.333g hydroxyethylidene diphosphonic acid, 1.666g sodium glucoheptonic acid, 0.25g sodium molybdate, 0.60g benzalkonium chloride, 0.50g didecyl dimethyl ammonium chloride (80%). Obtain a high-concentration peracetic acid stock solution that can be stored for a long time (peracetic acid concentration>100g / L, hydrogen peroxide concentration is 40g / L).

[0046] Evaluation of the sterilization effect of the peracetic acid composite disinfectant prepared in Example 2 and Example 1

[0047] The peracetic acid composite disinfectant in Example 1 of the present invention was subjected to a carrier immersion qualitative sterilization test in accordance with the "Technical Specifications for Disinfection" (2002 edition) and the "WS / T10009-2023 Disinfection Product Testing Method".

[0048] Test 1: Qualitative sterilization and neutralization agent identification test of disinfectant in Example 1 of the present invention

[0049] 1. Reagents and Materials Used

[0050] Test strain: Bacillus subtilis var. niger (ATCC 9372) spores.

[0051] Neutralizer: DE neutralizing broth;

[0052] Tryptone soy broth (TSB): weigh 30 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0053] Tryptone soy agar (TSA): weigh 40 g and add to 1000 mL of distilled water. Sterilize with pressure steam at 121°C for 15 min before use.

[0054] Diluent (TPS): 1 g / L tryptone and 8.5 g / L sodium chloride were added to 1000 mL of distilled water and sterilized by pressure steam at 121°C for 15 min before use;

[0055] Nutrient broth (NB) medium: weigh 18 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0056] Materials: test tube (1.8cm×18cm), carrier (cloth, 10mm×10mm), etc., sterilize and set aside.

[0057] 2. Experimental Grouping

[0058] Group 1: neutralizer broth + bacterial suspension;

[0059] Group 2: (disinfectant + neutralizer broth) + bacterial suspension;

[0060] Group 3: broth + bacterial suspension;

[0061] Group 4: bacterial suspension + culture medium;

[0062] Group 5: broth + diluent + culture medium.

[0063] 3. Operation procedures

[0064] The prepared peracetic acid composite disinfectant of Example 1 of the present invention was diluted to a concentration of 1000 mg / L (in terms of peracetic acid).

[0065] Take out the spore solution of Bacillus subtilis black variant stored in the refrigerator and dilute it with TSB to a bacterial count of 1×10 3 CFU / mL~1×10 4 CFU / mL spore suspension, the test includes 5 groups:

[0066] Group 1: Take two sterile test tubes and add 5 mL of DE neutralizer broth to each tube, then add 10 μL of spore solution to each tube, mix well, and place in a 36℃±1℃ incubator for 7 days to observe the results. Observe the ability of the neutralizer broth to restore the culture of a small amount of test bacteria;

[0067] Group 2: Take two sterile test tubes and add 5mL of DE neutralizer broth to each tube, then add a piece of cloth soaked in disinfectant to each broth to make neutralization product broth. After neutralization for 10 minutes, add 10μL of spore solution to each tube, mix well, and place in a 36℃±1℃ incubator for 7 days to observe the results. Observe the ability of the neutralization product broth to restore the culture of a small amount of test bacteria;

[0068] Group 3: Take two sterile test tubes, add 5 mL of TSB to each, then add 10 μL of spore solution to each, mix well, and place in a 36℃±1℃ incubator for 7 days to observe the results. Observe whether a small amount of test bacteria can grow normally in TSB broth;

[0069] Group 4: Pipette 10 μL of the test spore solution into two sterile plates, pour 15 mL to 20 mL of TSA into each plate, and place in a 36°C ± 1°C incubator for spore counting and culture. Count the total amount of spores in the test system;

[0070] Group 5: Take two sterile test tubes, add 5mL TSB to one and 5mL DE neutralizing broth to the other, place in a 36℃±1℃ incubator for 7 days and observe the results; take 1mL of the diluent into a sterile plate, pour 15mL~20mL of TSA used in the same batch of the test, place in a 36℃±1℃ incubator for 48h and observe the results. Observe whether the broth, culture medium, diluent, etc. used have bacterial growth.

[0071] 4. Evaluation regulations

[0072] When the test results meet all the following conditions, the selected neutralizer broth can be judged to be qualified.

[0073] All test tubes from Group 1 to Group 3 showed bacterial growth, and the broth was slightly turbid with wrinkled bacterial films.

[0074] The total number of spores in the Group 4 test system should be 10 CFU to 100 CFU.

[0075] Group 5 showed sterile growth.

[0076] The test was repeated 5 times and each test should meet the above conditions.

[0077] 5. Test results

[0078] As shown in Table 1, the test was repeated 5 times, and all test tubes in Groups 1 to 3 had bacterial growth. The total colony count in Group 4 was 44 CFU to 56 CFU, and there was no bacterial growth in Group 5. The test results of the five groups all met the requirements of the specification. This shows that the selected neutralizer can effectively neutralize the peracetic acid compound disinfectant, and the neutralizer and the neutralization product solution have no effect on the growth of Bacillus subtilis variant spores.

[0079] Table 1 Neutralizer identification test results

[0080]

[0081] Note: “+” indicates bacterial growth; “-” indicates sterile growth.

[0082] Test 2: Qualitative sterilization test of disinfectant carrier immersion in Example 1 of the present invention

[0083] 1. Reagents and Materials Used

[0084] Test strain: Bacillus subtilis var. niger (ATCC 9372) spores.

[0085] Neutralizer: DE neutralizing broth;

[0086] Tryptone soy broth (TSB): weigh 30 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0087] Tryptone soy agar (TSA): weigh 40 g and add to 1000 mL of distilled water. Sterilize with pressure steam at 121°C for 15 min before use.

[0088] Diluent (TPS): 1 g / L tryptone and 8.5 g / L sodium chloride were added to 1000 mL of distilled water and sterilized by pressure steam at 121°C for 15 min before use;

[0089] Nutrient broth (NB) medium: weigh 18 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0090] Test tube: 1.8cm×18cm, sterilized for later use;

[0091] Carrier: White plain cotton cloth, which should be degreased first. The degreasing method is as follows: ① Boil the carrier in water containing detergent for 30 minutes; ② Wash with tap water; ③ Boil with distilled water for 10 minutes; ④ Rinse with distilled water until the pH is neutral; ⑤ Dry and iron for use. Then, remove one warp and one weft yarn around the edge of the degreased cloth according to the size specified by the carrier, and then cut it into carriers of 10mm×10mm according to the yarn drawing marks, and sterilize it with pressure steam for use.

[0092] 2. Experimental Grouping

[0093] Test group: Bacillus subtilis var. niger (ATCC 9372) spore-stained tablets were selected, and the disinfectant concentration (calculated as peracetic acid) and action time were 250 mg / L, 20 min, 500 mg / L, 10 min, 750 mg / L, 5 min, 1000 mg / L, 2 min for testing;

[0094] Positive control group: Use standard hard water instead of disinfectant solution and perform the test according to the same steps as above. The result represents the concentration of bacterial solution in the test system, which is used as the concentration of live bacteria in the control group;

[0095] Negative control group: observe whether the relevant reagents and culture medium used in the same experiment are contaminated.

[0096] 3. Operation procedures

[0097] Preparation of stained slices: Spread the sterilized carrier slices flat on a sterile plate, and drip spore solution of Bacillus subtilis black variant (ATCC 9372) on each slice, with a dripping amount of 10 μL per slice. After dripping, the stained carrier can be placed in a 37°C incubator to dry (about 20 min to 30 min), or placed in the shade at room temperature to dry naturally before use. Make the number of recovered colonies on each bacterial slice 1×10 6 CFU / piece~5×10 6 CFU / tablet.

[0098] Preparation of the use liquid: dilute the prepared peracetic acid composite disinfectant described in Example 1 of the present invention to a concentration of 250 mg / L, 500 mg / L, 750 mg / L, and 1000 mg / L (calculated as peracetic acid).

[0099] Take a sterile plate and mark the concentration of the added disinfectant. Pipette 5.0 mL of disinfectant solution of corresponding concentration and add it to the plate. Place the plate containing disinfectant in a 20℃±1℃ water bath for 5 minutes. Use sterile tweezers to take 6 pre-prepared bacterial slices (2 slices at each time) and place them in the plate, and immerse them in the disinfectant of corresponding concentration. After the test bacteria and disinfectant interact for the set time, use sterile tweezers to take out the bacterial slices and transfer them to 5.0 mL TSB test tubes containing neutralizer. Mix with an electric mixer for 20 seconds as the test group sample.

[0100] Take another plate, add 20.0mL standard hard water instead of disinfectant, put in 4 bacterial tablets, act until the set time, take out 2 tablets, transfer them to 5.0mL TSB test tubes containing neutralizer, and the subsequent test steps are the same as the above test group, as the positive control group sample. Take out another 2 tablets, transfer them to 5.0mL diluent test tubes, count the live bacteria culture, and use them as the bacterial count control group sample.

[0101] Take one test tube containing 5.0 mL of TSB and one test tube containing 5.0 mL of neutralizer TSB, place them in a constant temperature incubator for incubation. This sample serves as a negative control.

[0102] All test samples were cultured in a constant temperature incubator at 36℃±1℃. The final results were observed after 7 days of broth culture in test tubes and 72 hours of culture on spore counting plates.

[0103] The experiment was repeated 5 times.

[0104] 4. Judgment criteria

[0105] Article 5.1.7.8.2 of "WS / T 10009-2023 Test Methods for Disinfection Products" stipulates that in the qualitative sterilization test for carrier immersion, there is bacterial growth in the positive control group, the bacterial count control group meets the requirements, and there is no sterile growth in the negative control group. If there is no sterile growth in all 5 tests, it is judged to be sterilization qualified.

[0106] 5. Test results

[0107] The peracetic acid disinfectant dilution of the present invention was used for carrier immersion qualitative sterilization test under the conditions of 250 mg / L for 20 min, 500 mg / L for 8 min, 750 mg / L for 5 min, and 1000 mg / L for 2 min. The results showed that bacteria grew in the positive control group, and the number of colonies in the bacterial control group was 1.64×10 6 CFU / piece~3.70×10 6 CFU / piece meets the requirements. The negative control group had no sterile growth, and the test group had no sterile growth in 5 tests, which can be judged as qualified for sterilization.

[0108] Table 2 Carrier immersion qualitative sterilization test results

[0109]

[0110] Experiment 3: Comparative study on the killing effect of the disinfectant of Example 1 of the present invention, similar domestic disinfectants and peracetic acid disinfectant prepared by phosphotungstic acid catalysis

[0111] 1. Reagents and Materials Used

[0112] Disinfectant: The disinfectant of Example 1 of the present invention has a peracetic acid content of 107.76 g / L and a hydrogen peroxide content of 42.88 g / L; similar disinfectant 1 is a binary peracetic acid disinfectant. According to the instruction manual, after adding liquid A to liquid B for activation for 24 hours, the peracetic acid content is 160.90 g / L and the hydrogen peroxide content is 280.74 g / L; similar disinfectant 2 is a monobasic peracetic acid disinfectant, with a peracetic acid content of 127.58 g / L and a hydrogen peroxide content of 149.95 g / L. The peracetic acid disinfectant prepared using phosphotungstic acid catalysis is called similar disinfectant 3, that is, the catalyst in the preparation method of Example 1 is replaced with phosphotungstic acid, and the remaining steps remain unchanged to obtain the disinfectant. The disinfectant has a peracetic acid content of 102.55 g / L and a hydrogen peroxide content of 41.36 g / L.

[0113] Test strain: Bacillus subtilis var. niger (ATCC 9372) spores.

[0114] Neutralizer: DE neutralizing broth;

[0115] Tryptone soy broth (TSB): weigh 30 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0116] Tryptone soy agar (TSA): weigh 40 g and add to 1000 mL of distilled water. Sterilize with pressure steam at 121°C for 15 min before use.

[0117] Diluent (TPS): 1 g / L tryptone and 8.5 g / L sodium chloride were added to 1000 mL of distilled water and sterilized by pressure steam at 121°C for 15 min before use;

[0118] Nutrient broth (NB) medium: weigh 18 g and add into 1000 mL distilled water, sterilize by pressure steam at 121°C for 15 min before use;

[0119] Materials: test tube (1.8cm×18cm), carrier (cloth, 10mm×10mm), etc., sterilize and set aside.

[0120] 2. Experimental Grouping

[0121] Test group: select Bacillus subtilis black variant (ATCC 9372) spore-stained tablets, disinfectant concentration 500mg / L (calculated as peracetic acid) and action time of 2.5min, 5.0min, 7.5min for testing;

[0122] Positive control group: Use standard hard water instead of disinfectant solution and perform the test according to the same steps as above. The result represents the concentration of bacterial solution in the test system, which is used as the concentration of live bacteria in the control group;

[0123] Negative control group: observe whether the relevant reagents and culture medium used in the same experiment are contaminated.

[0124] 3. Operation procedures

[0125] Prepare the spore-stained bacterial slides of Bacillus subtilis var. niger (ATCC 9372) for the test, so that the number of recovered colonies on each bacterial slide is 1×10 6 CFU / piece~5×10 6 CFU / tablet.

[0126] The composite peracetic acid disinfectant of Example 1, the binary peracetic acid disinfectant of the same disinfectant 1, the mono-peracetic acid disinfectant of the same disinfectant 2 and the mono-peracetic acid disinfectant of the same disinfectant 3 were diluted to 500 mg / L (in terms of peracetic acid) and placed in a 20°C±1°C water bath for standby use. In the actual reaction environment, the peracetic acid content of the original solution of Example 1 is 500 mg / L, and the hydrogen peroxide content is about 200 mg / L; the peracetic acid content of the binary peracetic acid disinfectant of the same disinfectant 1 is 500 mg / L, and the hydrogen peroxide content is about 875 mg / L; the peracetic acid content of the mono-peracetic acid disinfectant of the same disinfectant 2 is 500 mg / L, and the hydrogen peroxide content is about 625 mg / L; the peracetic acid content of the same disinfectant 3 is 500 mg / L, and the hydrogen peroxide content is about 200 mg / L.

[0127] Test group: Take a sterile plate and mark the type of disinfectant injected. Pipette the disinfectant solution of the corresponding concentration and inject it into the plate at a volume of 5.0 mL per piece. Place the plate containing the disinfectant in a 20℃±1℃ water bath for 5 minutes, use sterile tweezers to take 3 pre-prepared bacterial slices and place them in the plate, and immerse them in the disinfectant. After the bacterial solution and disinfectant interact for each set time, use sterile tweezers to take out the bacterial slices and transfer them to test tubes containing 5.0 mL of neutralizer. Mix with an electric mixer for 20 seconds, or vibrate the test tube on the palm of your hand 80 times, and neutralize for 10 minutes. After mixing, draw 1.0 mL and inoculate the plate directly. Inoculate 2 plates per tube to count the viable bacteria culture.

[0128] Positive control: Use standard hard water instead of disinfectant to conduct parallel test. The rest of the test steps are the same as the above test group. This group serves as the positive control.

[0129] Negative control: Pipette 1.0 mL of diluent and neutralizer into a sterile dish, and pour in 15 mL to 20 mL of culture medium from the same batch as a negative control sample.

[0130] All test samples were placed in a constant temperature incubator at 36°C ± 1°C for 72 hours and the final results were observed.

[0131] The test was repeated three times, and the number of viable bacteria in each group (CFU / tablet) was calculated and converted into a logarithmic value (N). The killing logarithm was then calculated according to the following formula:

[0132] Killing logarithm (KL) = logarithm of the average viable bacteria concentration in the control group (N0) - logarithm of the viable bacteria concentration in the test group (N x )

[0133] 4. Test results

[0134] Table 3 Comparison of the results of killing bacterial spores by Example 1 of the present invention and similar disinfectants

[0135]

[0136]

[0137] Note: The average logarithmic value and range of the positive control are 6.68 (6.64-6.71).

[0138] As shown in Table 3, the composite peracetic acid disinfectant of the present invention is diluted to a peracetic acid content of 500 mg / L and a hydrogen peroxide content of 200 mg / L for 5.0 min, and the average inactivation logarithm of Bacillus subtilis black variant spores is greater than 3.00, which can achieve efficient disinfection; the average inactivation logarithm of Bacillus subtilis black variant spores is greater than 6.00 for 7.5 min, reaching the sterilization level. The two domestic similar disinfectants have the same peracetic acid content as Example 1 and a hydrogen peroxide content that is 3-4 times higher. The average killing logarithm of Bacillus subtilis black variant spores for 7.5 min is greater than 3.00, and only achieves efficient disinfection effect. The killing effect of the peracetic acid disinfectant prepared by phosphotungstic acid catalysis on Bacillus subtilis black variant spores is similar to that of Example 1 of the present invention, but the average killing logarithm of Bacillus subtilis black variant spores for 7.5 min is less than 6.00, which fails to reach the sterilization level. The results show that the disinfection effect of Example 1 of the present invention is better than that of similar disinfectants.

[0139] Example 3: Determination of metal corrosion of the disinfectant prepared in Example 1 of the present invention

[0140] The composite disinfectant in Example 1 of the present invention was subjected to a metal corrosion test in accordance with the Technical Specification for Disinfection (2002 edition) and GB / T 38498-2020.

[0141] 1. Materials used

[0142] Metal sheet: round, diameter 24±0.1mm, thickness 1.0mm, center hole diameter 2.0mm, total surface area approximately 9.80cm 2 . The finish is 4 to 6. The raw materials are as follows: carbon steel (GB700-65), stainless steel (GB1220-75), copper (GB2060-80), aluminum (GB1173-74).

[0143] Soaking container: glass, with lid, capacity 800ml~1000ml.

[0144] Sandpaper: 120 grit water-repellent sandpaper, GB 2477.

[0145] Weighing cup.

[0146] Balance: Sensitivity 0.1mg.

[0147] 2. Test procedures

[0148] First, soak four kinds of metal sheets, 3 pieces of each, in a surfactant detergent for 10 minutes, fully degrease, and wash; use 120-grit water sandpaper to remove the oxide layer on both sides and the surrounding surface of the metal sheet, and then rinse with tap water. Degrease again with anhydrous ethanol, dry in a 50℃ constant temperature box for 1 hour, and weigh after the temperature drops to room temperature. After the balance returns to zero, weigh each metal sheet 3 times, accurate to 0.1mg, and take the average value as the weight before the test. When weighing, wear clean gloves and do not touch the sample directly with your hands.

[0149] Dilute the stock solution of peracetic acid compound disinfectant to the highest concentration of 1000mg / L, take 600ml of the diluted disinfectant into a 1000ml ground-mouth reagent bottle; soak 3 pieces of the same metal sheet in every 600ml disinfectant, with each sample separated by more than 1cm; cover the ground-mouth bottle cap of the reagent bottle and soak for 72h; set up a control of stainless steel soaked in distilled water at the same time; after soaking for the specified time, take out the metal sheet, rinse it with tap water first, and then use a brush or other soft tools to remove the corrosion products; after removing the corrosion products and cleaning the metal sample, use coarse filter paper to absorb the water, place it in a plate padded with filter paper, put it in a 50℃ incubator, dry it for 1h, pick it up with tweezers, and weigh it on the balance after the temperature drops to room temperature; weigh it 3 times after the balance returns to zero, and take its average value as the weight after the test. When weighing, as before the test, you should wear clean gloves and do not touch the sample directly with your hands (the same below).

[0150] When using chemical methods to remove corrosion products from samples, a corresponding blank control is required to correct the error. The blank control samples are treated with the same surface treatment, cleaned and weighed as the test group samples, but are not soaked in disinfectants. Afterwards, they are treated with chemicals, rinsed with water, dried, weighed, and their average weight loss is calculated in the same way as the test group samples.

[0151] During the whole process of the test, a stainless steel sheet soaked in distilled water should be set up as a control, and the weight difference before and after soaking should be less than 0.3 mg. Otherwise, after finding the cause, all tests should be repeated.

[0152] Test results, observe and record the color change of the metal sheet, and express it as the average value of the metal corrosion rate (R). When calculating, the weight loss value of the blank control group sample should be subtracted. The calculation formula is as follows:

[0153]

[0154] R is the corrosion rate, mm / a (millimeter / year); m is the weight of the metal sheet before the test, g; m t is the weight of the metal sheet after the test, g; m k The weight loss value of the sample after chemical treatment to remove corrosion products, g. If no chemical removal treatment is performed in the test, m is deleted from the formula during calculation. k Value; S is the total surface area of ​​the metal sheet, cm2 ; t is the test time, h; d is the density of the metal material, kg / m 3 .

[0155] 3. Corrosivity classification standards

[0156] Table 4 Corrosivity classification standards

[0157] Corrosion rate R(mm / a) level <0.0100 Almost no corrosion 0.0100～<0.100 Mild corrosion 0.100～<1.00 Moderate corrosion ≥1.00 Severe corrosion

[0158] 4. Experimental results

[0159] As shown in Table 5-1, the corrosion rate of stainless steel at the highest concentration of 1000 mg / L of the peracetic acid composite disinfectant is basically no corrosion, the corrosion rate of aluminum is mild corrosion, and the corrosion rate of carbon steel and copper is severe corrosion. Compared with the peracetic acid composite disinfectant of the present invention, the peracetic acid disinfectant prepared using phosphotungstic acid has a higher corrosion rate on carbon steel and copper.

[0160] Table 5-1 Corrosion degree of metal by peracetic acid composite disinfectant of the present invention

[0161]

[0162] Table 5-2 Corrosion degree of metals by peracetic acid disinfectant prepared using phosphotungstic acid

[0163]

[0164] Example 4. Stability evaluation of the disinfectant prepared in Example 1 of the present invention

[0165] The composite disinfectant of Example 1 of the present invention was evaluated for stability in accordance with the "Technical Specification for Disinfection" (2002 edition) and "GBT 38499-2020 Disinfectant Stability Evaluation Method".

[0166] 1. Test methods

[0167] Accelerated test: The composite disinfectant stock solution prepared in Example 1 was placed in a constant temperature box at 37°C ± 2°C for 90 days, and the peracetic acid content in the disinfectant before and after storage was determined by a chemical method.

[0168] 2. Evaluation criteria

[0169] After being stored in a constant temperature box at 37℃±2℃ for 90 days, the decrease rate of peracetic acid content before and after storage is ≤15%, and the content of active ingredients after storage is not less than the lower limit of the content specified in the product. The shelf life of the product is determined to be at least 2 years when stored at room temperature.

[0170] 3. Experimental results

[0171] The test was repeated 3 times and stored in a 37°C ± 2°C incubator for 90 days. The range of the decrease rate of the peracetic acid content before and after storage was 6.68% to 7.27%, which met the requirement of an unstable product decrease rate of ≤15%. As shown in Table 6, the addition of stabilizers of 3.333 g / L hydroxyethylidene diphosphonic acid and 1.666 g / L sodium glucoheptonate can ensure that the composite peracetic acid disinfectant prepared by the present invention can be stored for at least 2 years at room temperature.

[0172] Table 6 Stability test results of composite disinfectant of Example 1

[0173]

[0174]

Claims

1. A high-concentration stable peracetic acid compound disinfectant, consisting of the following components in percentage by weight: Peracetic acid 10-20%, hydrogen peroxide 2-10%, corrosion inhibitor 0.05-1%, stabilizer 0.1-1% and the balance deionized water.

2. The compound disinfectant according to claim 1, characterized in that: The peracetic acid is obtained by catalyzing acetic acid with the following catalyst: One or two of 1-pentyl-3-methylimidazolium phosphotungstate, 1-butyl-3-methylimidazolium phosphotungstate and phosphotungstic acid.

3. The compound disinfectant according to claim 1 or 2, characterized in that: The corrosion inhibitor is one or more of laurylamine dipropylene diamine, carboxylic acid type α-iminoacetic acid, quaternary ammonium salt, sodium molybdate, fatty alcohol polyoxyethylene ether, potassium sorbate and sodium silicate.

4. The composite disinfectant according to any one of claims 1 to 3, characterized in that: The stabilizer is one or more of citric acid, hydrolyzed polymaleic anhydride, sodium tripolyphosphate, hydroxyethylethylenediaminetriacetic acid, disodium nitrilotriacetate, ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, sodium glucoheptanoate, polyoxyethylene ether and phosphoric acid.

5. The compound disinfectant according to claim 3, characterized in that: The quaternary ammonium salt is selected from at least one of the following: a single-chain quaternary ammonium salt and a double-chain quaternary ammonium salt. The single-chain quaternary ammonium salt is an alkyl dimethyl benzyl ammonium halide, and its structural formula is shown in Formula I: In formula I, n=8-18, X=Br - or Cl - ; The double-chain quaternary ammonium salt is a dialkyl dimethyl ammonium halide, and its structural formula is shown in Formula II: In formula II, m and n each independently represent an integer of 8 or 10, and X = Br - or Cl - .

6. The composite disinfectant according to any one of claims 1 to 5, characterized in that: The composite disinfectant is made of the following components in percentage by mass:

7. A method for preparing the compound disinfectant according to any one of claims 1 to 6, comprising the steps of: mixing hydrogen peroxide, acetic acid and a catalyst, stirring for 6 to 24 hours, then adding a stabilizer and a corrosion inhibitor and stirring evenly, and filtering to remove the catalyst.

8. Use of the compound disinfectant according to any one of claims 1 to 6 as a sterilizing agent in the following: 1) Used for high-level disinfection and sterilization of heat-labile medical devices; 2) Used for high-level disinfection and sterilization in high-level biosafety laboratories, high-risk infectious disease foci, and biosafety incident sites to kill bacterial spores, viruses, bacterial propagules, and fungi in the air and on the surface of objects, and achieve a sterilization effect.

9. The use according to claim 8, characterized in that: The compound disinfectant is used in the form of liquid immersion, spraying, atomization and gas fumigation.

10. The use according to claim 8 or 9, characterized in that: The bacterial spores are selected from at least one of the following: Bacillus anthracis spores, Bacillus subtilis var. niger spores, Bacillus stearothermophilus spores, and Bacillus cereus spores; The virus comprises an enveloped virus and a non-enveloped virus, and is selected from at least one of the following: polio virus, HIV, mad cow virus, Creutzfeldt-Jakob virus, new coronavirus, hand, foot and mouth disease virus, avian influenza virus, influenza A (H1N1) virus and influenza A (H7N9) virus; The bacteria and fungi are selected from at least one of the following: intestinal pathogens, pyogenic cocci, pathogenic yeasts, common pathogens of hospital infections and drug-resistant bacteria.

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