A kind of Peracetic acid composite disinfectant and preparation method thereof
Technical field
The present invention relates to peroxyacetic acid disinfectant fields, more particularly to stable peroxyacetic acid disinfectant.
Background technique
There are a large amount of microorganism in the environment that we live, some are beneficial, some are harmful.Once harmful microorganism is big
Amount exists, and will lead to many communicable diseases and largely wreaks havoc prevalence, damages the health of people and animal.Therefore, environment is carried out
The inevitable choice of human health is just protected in disinfection treatment at one.
Currently, being divided into two classes about disinfection treatment method.One kind is physical method, including is boiled, high pressure steam sterilization,
Ultraviolet light irradiation, sterilization by ionizing radiation etc..One kind is chemical method, refers mainly to be sprayed with disinfectant, spraying to sterilize, this
A little disinfectants include: quick lime, caustic soda, ethyl alcohol, glutaraldehyde, Iodophor, formalin, disinfectant phenolic, chlorine-containing disinfectant and mistake
Fluoroacetic acid disinfectant etc..For people's lives overall situation, physical method obviously be cannot meet the needs.And chemical disinfection
In, other than chlorine-containing disinfectant and peroxyacetic acid disinfectant, other disinfectants or inefficient or environment are unfriendly, cannot
Meets the needs of people are to environment disinfected.But chlorine-containing disinfectant and peroxyacetic acid disinfectant are extremely unstable, not shelf-stable.Therefore,
Studying stability high chlorine-containing disinfectant and peroxyacetic acid disinfectant becomes the inevitable choice of people.
It is worth noting that, Peracetic acid has wide spectrum, efficiently, decomposition product is nontoxic low fatty acid, water and oxygen
The advantages that gas, will not leave behind any harmful substance using peracetic acid disinfectant.Therefore the antiseptic property of Peracetic acid and its superior
Environmental compatibility also increasingly paid attention to.
For peroxyacetic acid disinfectant, since Peracetic acid has corrosivity, ideal peroxyacetic acid disinfectant is
In the case where peroxyacetic acid concentration is lower namely disinfectant waits the biggish situation of extension rate when in use, meet not to being sterilized
In the case that object generates corrosiveness, there is quick sterilization Disinfection Effect.
Summary of the invention
Present invention aims at a kind of high stability peroxyacetic acid disinfectant in view of the deficiencies of the prior art, is provided, this disappears
Toxic agent has the effect of quick sterilization disinfection at low concentrations, while having both preferable stability.
In order to solve the above technical problems, the present invention provides a kind of Peracetic acid composite disinfectant, by hydrogen peroxide, glacial acetic acid,
Sodium pyrophosphate, the concentrated sulfuric acid, nonionic surface active agent are formulated, when preparation, effective component hydrogen peroxide in hydrogen peroxide
Quality and glacial acetic acid mass ratio are greater than 1, keep hydrogen peroxide excessive, preferably (1-6): 1.
Further, the mass ratio of the hydrogen peroxide effective component in the hydrogen peroxide and glacial acetic acid is (2-3): 1.
Further, the peroxyacetic acid disinfectant is formulated by following raw materials according according to weight:
Wherein, the number is mass parts.
Preferably, the weight of each component is as follows in the high stability peroxyacetic acid disinfectant raw material:
Wherein, the number is mass parts.
Further, the weight of each component is as follows in the high stability peroxyacetic acid disinfectant raw material:
Further, the nonionic surface active agent is selected from least one of tween 70, Tween 80, Span, excellent
It is selected as Tween 80.
Surfactant is divided into cationic surfactant, anionic surfactant and nonionic surface active agent
Three categories.Wherein cationic surfactant is widely used in disinfection and sterilization, and anionic surfactant is mainly used as detergent.
These two types of surfactants are dissociated into cation and anion respectively upon dissolution, and the cationic stabilization to Peracetic acid is not
Benefit easily accelerates Peracetic acid cracking, lowers its Disinfection Effect.Nonionic surface active agent is not cracked into ion upon dissolution.
The present invention uses nonionic surface active agent, is mainly used for phase transfer in system, so that wellability and adhesion are improved,
And reduce decomposition of peracetic acid.Tween 70, Tween 80, Span are nonionic surface active agent, can be played in system
Improve wellability and adhesion effect.Wherein, Tween 80 dissolubility is relatively more preferable, living as non-ionic surface in the present invention
Property agent it is preferred.
Further, the sodium pyrophosphate is selected from anhydrous sodium pyrophosphate or/and sodium pyrophosphate decahydrate, preferably anhydrous coke
Sodium phosphate.
Further, the hydrogen peroxide is selected from 27.5% hydrogen peroxide or/and 35% hydrogen peroxide.
It is presently commercially available sell commodity hydrogen peroxide with hydrogen peroxide mass concentration be 27.5% and 35% it is most commonly seen be easy to get,
It therefore is preferably the hydrogen peroxide of both concentration.The concentration and dosage of hydrogen peroxide are without strict demand and limitation, palpus in the present invention
It is determined with the mass ratio of effective component hydrogen peroxide therein and glacial acetic acid.In the present invention program, a large amount of mistakes of hydrogen peroxide
Amount, make effective component hydrogen peroxide therein with glacial acetic acid mass ratio (1-6): 1, preferably (2-3): 1, hydrogen peroxide
It is excessive, it is sufficiently reacted with acetic acid and generates Peracetic acid, Peracetic acid active constituent content is high in obtained disinfectant, hydrogen peroxide
It is present in disinfectant system with Peracetic acid with certain proportion, is conducive to improve stability.Meanwhile Peracetic acid and peroxide
Change hydrogen and ionize out peroxide radical ion in aqueous solution, is conducive to the concentration for improving peroxide radical ion in disinfectant.And peroxide second
The dissipation effect of acids disinfectant mainly discharges elemental oxygen by Peracetic acid, and carries out irreversible oxidation to harmful microorganism
It kills, improves peroxide root concentration in disinfectant, be conducive to improve sterilization effect.Experiments have shown that peroxidating in disinfectant
Hydrogen, Peracetic acid exist simultaneously, and mass ratio generates optimal bactericidal effect at 5: 1 or so, and and with higher steady
Qualitative (see specific embodiment part).Meanwhile acetic acid sufficiently reacts away and can avoid too strong sour corrosion disinfector.
The present invention also provides the preparation methods of above-mentioned high stability peroxyacetic acid disinfectant, include the following steps:
According to formula ratio, sodium pyrophosphate is added into hydrogen peroxide, glacial acetic acid is added after sodium pyrophosphate dissolution and is stirred
Uniformly, the concentrated sulfuric acid is added, stirring is reacted at room temperature, and non-ionic table is added into gained reaction solution after the reaction was completed
Face activating agent stirs evenly up to peroxyacetic acid disinfectant.
Further, reaction time 20-30h.
With prior art ratio, the invention has the following advantages:
1. disinfectant of the present invention is prepared, by hydrogen peroxide excess, in obtained disinfectant, hydrogen peroxide and peroxide second
Acid is present in disinfectant system with certain proportion, have excellent quick sterilization Disinfection Effect, to staphylococcus aureus,
Escherichia coli, C.perfringens and pseudomonas aeruginosa can effectively be killed, and can reach in 5 minutes and to kill completely
Effect has the advantages that sterilize applied widely, quick sterilization.In use, the concentration item of thimerosal of the invention 0.2%
The bactericidal effect that Disinfection Effect is much better than under commercially available 0.2% concentration conditions of STORING STABILITY OF PERACETIC ACID IN BINARY PACKING disinfectant is thought under part, is reached
Consistent bactericidal effect under commercially available 0.8% concentration conditions of STORING STABILITY OF PERACETIC ACID IN BINARY PACKING disinfectant, achieves unexpected effect
Fruit (see the test of specific embodiment part sterilization effect)
2. disinfectant of the present invention, preparation when, is excessive with respect to glacial acetic acid by hydrogen peroxide, reacts glacial acetic acid completely
Pass through selection to Peracetic acid more importantly hydrogen peroxide and Peracetic acid are present in disinfectant system with certain proportion
Sodium pyrophosphate stabilizer, nonionic surface active agent Tween 80 reduce decomposition of peracetic acid, in combination with each raw material component
The adjusting of proportion, and have and be significantly better than the stability of existing peroxyacetic acid disinfectant, can long term storage (see specific reality
Apply the test of mode segmental stability).
3. the preparation process of peroxyacetic acid disinfectant of the present invention is simple, production cost is low, is suitble to large-scale production,
With industrial production application value.
Specific embodiment
High stability peroxyacetic acid disinfectant of the present invention is described further below by specific embodiment.With
Lower described only the embodiment of the present invention, is not intended to limit the scope of the invention, all using in description of the invention
Equivalent structure or equivalent flow shift made by holding, is applied directly or indirectly in other relevant technical fields, and similarly wraps
It includes in scope of patent protection of the invention.
Embodiment 1
27.5% hydrogen peroxide 22.5kg is weighed, anhydrous sodium pyrophosphate 50g is added, after sodium pyrophosphate is completely dissolved mixing,
Be added glacial acetic acid 2.5kg, after mixing is sufficiently stirred, be added concentrated sulfuric acid 10mL, after stirring and evenly mixing, at room temperature react 24 hours, instead
After answering, Tween 80 10mL is added, after mixing, bottles to get disinfectant of the present invention.
Embodiment 2
27.5% hydrogen peroxide 20.0kg is weighed, anhydrous sodium pyrophosphate 30g is added, after sodium pyrophosphate is completely dissolved mixing,
Be added glacial acetic acid 1.5kg, after mixing is sufficiently stirred, be added concentrated sulfuric acid 3mL, after stirring and evenly mixing, at room temperature react 20 hours, instead
After answering, Tween 80 3mL is added, after mixing, bottles to get disinfectant of the present invention.
Embodiment 3
27.5% hydrogen peroxide 25.0kg is weighed, anhydrous sodium pyrophosphate 70g is added, after sodium pyrophosphate is completely dissolved mixing,
Glacial acetic acid 3.5kg is added, after mixing is sufficiently stirred, concentrated sulfuric acid 17.5mL is added, after stirring and evenly mixing, reacts 30 hours at room temperature,
After completion of the reaction, Tween 80 21mL is added, after mixing, bottles to get disinfectant of the present invention.
Embodiment 4
27.5% hydrogen peroxide 22.0kg is weighed, anhydrous sodium pyrophosphate 40g is added, after sodium pyrophosphate is completely dissolved mixing,
Be added glacial acetic acid 2.0kg, after mixing is sufficiently stirred, be added concentrated sulfuric acid 10mL, after stirring and evenly mixing, at room temperature react 24 hours, instead
After answering, Tween 80 6mL is added, after mixing, bottles to get disinfectant of the present invention.
Embodiment 5
27.5% hydrogen peroxide 23.0kg is weighed, anhydrous sodium pyrophosphate 60g is added, after sodium pyrophosphate is completely dissolved mixing,
Be added glacial acetic acid 3.0kg, after mixing is sufficiently stirred, be added concentrated sulfuric acid 9mL, after stirring and evenly mixing, at room temperature react 24 hours, instead
After answering, Tween 80 15mL is added, after mixing, bottles to get disinfectant of the present invention.
The investigation of peroxyacetic acid disinfectant bactericidal effect to above embodiments preparation and stability below.
One, sterilization effect is tested
1. test material
Disinfectant prepared by the embodiment of the present invention 1 (carries out assay when use.It is dense that quality is diluted to Sterile Hard Water
The sample for spending 0.2% concentration (using disinfectant as solute) is tested), 18.2% two-component packaging type peroxyacetic acid disinfectant (makes
Prepared with first 24 hours, when use carries out assay, is tested with the sample that Sterile Hard Water is diluted to 0.8% concentration),
Sterile Hard Water, agar medium contain the physiological saline (as dilution) of tryptone (mass concentration 0.1%), cow's serum
Albumin solution, staphylococcus aureus (ATCC 6538), Escherichia coli (8099), C.perfringens (ATCC
13124), pseudomonas aeruginosa (ATCC15442).
2. sterilize experimental method
(1) it is separately cultured, the above bacterium colony is taken to be inoculated with nutrient agar slopes culture respectively, it will fresh slant culture for 24 hours
With lawn on tryptone physiology salt washing lower inclined plane, mixes well, be prepared into bacteria suspension respectively.By bacteria suspension cow's serum
Albumin solution dilution, being configured to bacteria containing amount respectively is 1 × 107~5 × 107(bacteria suspension is dense for cfu/mL experimental concentration bacteria suspension
Degree: Escherichia coli are 4.5 × 107Cfu/mL, staphylococcus aureus 2.3 × 107Cfu/mL, clostridium perfringens 2.5 ×
107Cfu/mL, pseudomonas aeruginosa 4.8 × 107cfu/mL.).Constant temperature is carried out to thimerosal and bacteria suspension in 20 DEG C of water-baths.
(2) 1.25 times of disinfectant final concentration (disinfectants of final concentration of 0.2%) of disinfectant are added in sterile test tube
4.0mL adds bacteria suspension 1.0mL, mixes.Respectively effect different time 2,5, after ten minutes, take 0.5mL to mix sample liquid
It is added in the test tube of the dilution containing 4.5mL and mixes 10 minutes.Positive control is dilution, and thimerosal is not added.
(3) it takes 1.0mL sample liquid and positive control solution to be inoculated on agar medium plate respectively, sets 37 DEG C of culture 48h and do
Count plate calculates killing rate, and every group of test is repeated 3 times, and results are averaged, and test result is shown in Table 1.
The killing effect of 1 Peracetic acid composite disinfectant of table and reference substance to bacterium in suspension
Note: test temperature is 20 DEG C, bacteria suspension concentration: Escherichia coli are 4.5 × 107Cfu/mL, staphylococcus aureus
2.3×107Cfu/mL, clostridium perfringens 2.5 × 107Cfu/mL, pseudomonas aeruginosa 4.8 × 107cfu/mL.It as a result is 3
Secondary test average value.
Above-mentioned test result show thimerosal of the invention under 0.2% concentration conditions with commercially available two-component packaging peroxide
Bactericidal effect under 0.8% concentration conditions of acetic acid is consistent.It is much better than under commercially available 0.2% concentration conditions of STORING STABILITY OF PERACETIC ACID IN BINARY PACKING
Bactericidal effect.Illustrate thimerosal of the present invention due to hydrogen peroxide, Peracetic acid generate synergistic function (in embodiment 1,
Hydrogen peroxide, Peracetic acid generate the effect of optimum synergistic synergy fruit in mass ratio 5: 1).In thimerosal use process of the present invention,
100.00% was all reached to the eradicative rate of all kinds of bacteriums in 5 minutes, it is believed that achieve the effect that kill completely, and to golden yellow
Staphylococcus, Escherichia coli, C.perfringens and pseudomonas aeruginosa can useful effects.
It can be seen that thimerosal bactericidal effect of the present invention is very good, to staphylococcus aureus, Escherichia coli, gas pod is produced
Film clostridium and pseudomonas aeruginosa can effectively be killed, and can achieve the effect that kill completely in 5 minutes, have sterilization suitable
With the advantages of range is wide, quick sterilization.And thimerosal of the invention has just reached commercially available binary under 0.2% concentration conditions
Pack consistent bactericidal effect under 0.8% concentration conditions of Peracetic acid.
Two, stability test
1. test material
2mol/L sulfuric acid, 100g/L liquor kalii iodide, 0.01mol/L liquor potassic permanganate, 100g/L manganese sulfate solution,
30g/L ammonium molybdate solution and 5g/L starch solution.It prepares and demarcates 0.05mol/L sodium thiosulfate titrating solution.
2. stability test
Measuring method method referring to as defined in 2002 version " disinfection technology standard " carries out.Precision is drawn the present invention and is implemented
Disinfectant made from example 1 is appropriate, makes it equivalent to Peracetic acid about 0.29g, is diluted in 100mL volumetric flask with distilled water
Scale mixes.Into 100mL iodine flask plus 2mol/L sulfuric acid 5mL, 100g/L manganese sulfate solution 3 drips, and mixing is added in precision
Peracetic acid dilution 5.0mL shakes up and is titrated to solution pinkiness with 0.01mol/L liquor potassic permanganate.Immediately plus
100g/L liquor kalii iodide 10mL and 30g/L ammonium molybdate 3 drip, and shake up and (are loaded on 0.05mol/L sodium thiosulfate titrating solution
In 25mL buret) be titrated to it is faint yellow.Then the drop of 5g/L starch solution 3 (solution becomes blue immediately) is added, continues with thio
Sodium sulphate is titrated to blue disappearance, records total dosage of sodium thiosulfate titrating solution.It repeats to survey 2 times, 2 average values is taken to carry out
It calculates.
Using accelerated test, by the peroxyacetic acid disinfectant stoste sealed package, 3 parts of a formula is placed in 54 DEG C of baking ovens and deposits
It puts 12 days.In storage front and back different time points sampling (wherein using commercially available binary form thimerosal 24 hours as 0 day after preparation)
Peroxide radical content is measured, quality stability is compared.Test result is shown in Table 2.
The peroxide radical content of 2 embodiment of the present invention of table, 1 thimerosal and commercially available binary form thimerosal under the conditions of 54 DEG C it is steady
Qualitative comparison (n=2).
Above-mentioned test result is it is found that be 21.52% when Peracetic acid content 0 day in thimerosal of the invention, at 54 DEG C
Higher temperature under constant temperature save 12 days after, Peracetic acid content still has 20.02%, and rate of descent is only 6.50%, illustrates this hair
Bright thimerosal stability is fine.And in commercially available binary form peroxide root thimerosal Peracetic acid content by 0 day be 7.67%,
After constant temperature saves 12 days at 54 DEG C, Peracetic acid content sharply falls to 3.81%, and rate of descent is up to 50.41%, table
The bright commercially available peracetic acid disinfectant stability is very poor.In general, its higher natural decomposition speed of peroxyacetic acid concentration
It is faster, and thimerosal of the invention is much larger than the Peracetic acid of commercially available binary form peracetic acid disinfectant in peroxyacetic acid concentration
In the case where concentration, the speed of decomposition of peracetic acid is far smaller than the decomposition rate of commercially available binary form peracetic acid disinfectant, says
Bright peroxyacetic acid disinfectant of the present invention has significant high stability.
Thimerosal of the invention is shown compared to commercially available product by above-mentioned testing result, stability greatly improves.Also,
According to this test, the validity period for predicting that thimerosal of the invention can stablize preservation 1.5 years at room temperature can be derived
(drop to < 10% with Peracetic acid content and be determined as that disinfectant fails), which is significantly larger than existing in the market
Peroxyacetic acid disinfectant.