CN102090393A - Stable peroxyacetic acid disinfectant - Google Patents
Stable peroxyacetic acid disinfectant Download PDFInfo
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- CN102090393A CN102090393A CN2010106109974A CN201010610997A CN102090393A CN 102090393 A CN102090393 A CN 102090393A CN 2010106109974 A CN2010106109974 A CN 2010106109974A CN 201010610997 A CN201010610997 A CN 201010610997A CN 102090393 A CN102090393 A CN 102090393A
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- disinfectant
- molybdate
- peracetic acid
- hydrogen peroxide
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Abstract
The invention discloses a stable peroxyacetic acid disinfectant which relates to a disinfectant. The peroxyacetic acid disinfectant comprises the following raw materials in percentage by mass: 27-39 percent of hydrogen peroxide, 22-36 percent of acetic acid, 0.01-2 percent of compound stabilizer, 0.01-2 percent of surfactant and the balance of water. In the prepared peroxyacetic acid disinfectant, the concentration of the peroxyacetic acid is 15-20 g/100g, the concentration of the hydrogen peroxide is 20-30 g/100g, and the concentration of the acetic acid is 10-20 g/100g. The peroxyacetic acid disinfectant has the characteristics of high peroxyacetic acid concentration, high stability, good disinfection and sterilization effects, simple production process, safety and the like.
Description
[technical field]
The present invention relates to a kind of disinfectant, relate in particular to a kind of stable peroxyacetic acid disinfectant, belong to the chemosterilant field.
[background technology]
As disinfectant, Peracetic acid (C
2H
4O
3) possess advantages such as wide spectrum, efficient, quick-acting, catabolite nontoxic residue-free, as far back as 20th century the forties just be used for sterilization, China just generally applies at the seventies.But generally Peracetic acid is very unstable, and factors such as temperature, illumination, alkali, organic matter, metal ion all can cause its concentration to descend rapidly.Present commercially available Peracetic acid product has two types: a kind of is binary form, and its product is divided into A, B two components, separately deposits at ordinary times, before using A, B component is mixed according to a certain percentage, places and is diluted to the desired concn use after 24 hours to 48 hours again.Mixed Peracetic acid concentration descends very fast, and this downward trend is accelerated with the raising of Peracetic acid concentration.In actual applications, can only measure the preparation Peracetic acid as required, make troubles, limit the application of Peracetic acid to use; A kind of is unary form, and the unary form Peracetic acid has overcome some defectives of binary form Peracetic acid, but its stability is sterilization circle one big technical barrier always.
External suitability for industrialized production Peracetic acid adopts hydrogen peroxide, glacial acetic acid as main raw material(s) more.The manufacturer mainly contains Degussa company, the Kemria company of FMC Corp., Solvay company, the Germany of the U.S., the Akzo Nobel company of Holland etc.Representative Peracetic acid trade name has the Vigorox of FMC Corp., the Proxitane of Solvary company, Peraclean of Degussa company or the like.It is raw material that the new patent of Germany Kemira company adopts hydrogen peroxide, glacial acetic acid, sulfuric acid is catalyzer, pyridinedicarboxylic acid is a stabilizing agent production Peracetic acid, its production technology adopts destilling tower, input hydrogen peroxide, acetic acid, sulfuric acid, pyridinedicarboxylic acid mixture at the bottom of the tower, the equilibrium liquid vaporization that generates at the bottom of the tower is after the inner-tower filling material distillation, can obtain target product distillating through the overhead condenser condensation, and reflux liquid also can be used as finished product and uses at the bottom of the tower after the alkali neutralisation treatment.Holland Akzo Nobel house journal adopts the continuous still tower process, hydrogen peroxide and acetic acid are sent into reactor by storage tank continuously through pump, the equilibrium liquid that generates enters destilling tower continuously, and by decompression distillation, overhead distillate flows out through condenser condenses and promptly obtains finished product.Germany MGC house journal is with acetic anhydride and hydroperoxidation, is lower than the Peracetic acid equilibrium liquid that the molal quantity of water in the hydrogen peroxide obtains higher concentration by control acetic anhydride molal quantity, adopts sulfuric acid as catalyzer in the reaction.Other adds amino carboxylic acid or organic phospho acid is made stabilizing agent.The Peracetic acid product contains stabilizing agent mostly, and the most frequently used is pyridinedicarboxylic acid.Akzo Nobel house journal adopts pyridinedicarboxylic acid and organic phospho acid to make mixed stabilizer, the collaborative stablizing effect that produces.In the Solvay house journal, for improving Stability of Acetic acid peroxide, add the fat alcohol ethoxyl compound wetting agent, additive not only can improve product stability, also can improve its wetability, promotes disinfectant to contact with the surface, improves Disinfection Effect.In the Japan Daicel house journal, the metal impurities with in the H type cationic ion-exchange resin removal Peracetic acid product can obviously improve product stable storage degree.Though these patented technologies the concentration that improves Peracetic acid and stable aspect differ from one another, its complex manufacturing, the manufacturing cost height, safety and stablization still can't satisfy produces and instructions for use.
[summary of the invention]
At the problem that present peroxyacetic acid disinfectant exists, the invention provides a kind of Peracetic acid concentration height, good stability, sterilization effect and reach simple, the safe peroxyacetic acid disinfectant of production technology well.
Peroxyacetic acid disinfectant of the present invention, each raw material mass percent is: hydrogen peroxide: 27-39%, acetate: 22-36%, compound stabilizer: 0.01-2%, surfactant: 0.01-2%, all the other are water.The mass concentration of Peracetic acid is 15-20g/100g in the prepared peroxyacetic acid disinfectant, hydrogen peroxide: 20-30%, acetate: 10-20%.
Preferably, each raw material mass percent is: hydrogen peroxide: acetate 34%: compound stabilizer 30%: surfactant 1%: 1%, and all the other are water.The mass concentration of Peracetic acid is 20g/100g in the prepared peroxyacetic acid disinfectant.
Preferably, described compound stabilizer is made up of tungstates or molybdate, organic phosphorus compound, benzenetricarboxylic acid, and its consumption (weight) is than being 1: 1: 2.
Preferably, described tungstates can be a kind of in sodium tungstate, potassium tungstate, tungstate lithium and the ammonium tungstate etc.
Preferably, described molybdate can be a kind of in sodium molybdate, potassium molybdate, lithium molybdate and the ammonium molybdate etc.
Preferably, described organic phosphorus compound can be a kind of in ethylenediamine tetraacetic methyl acid phosphate, hydroxy-methylbenzene fork diphosphonic acid, hydroxyl ethane fork diphosphonic acid, diethylenetriamine five methene phosphoric acid, the dimethylamino methane fork diphosphonic acid etc.
Preferably, described benzenetricarboxylic acid can be 1,2,3-benzene-1,1,3,5-1,3,5-Benzenetricarboxylic acid, 1,2, a kind of in the 4-trimellitic acid etc.
Described surfactant can be a kind of in the isomery alcohol ether non-ionic surface active agents such as isomery ten pure APEOs, isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether.
Peroxyacetic acid disinfectant of the present invention, concrete preparation method is as follows:
1. take by weighing tungstates or molybdate, organic phosphorus compound, benzenetricarboxylic acid and fully mix by 1: 1: 2 part by weight and make compound stabilizer.
2. prepare raw material by following part by weight: in every 100g peroxyacetic acid disinfectant, hydrogen peroxide: 27-39g, acetate: 22-36g, compound stabilizer: 0.01-2g, surfactant: 0.01-2g, all the other are water.
3. water is pumped in the enamel jacket reactor, add stirring and dissolving behind compound stabilizer and the surfactant, pump into hydrogen peroxide, acetate more successively, stirred 30 minutes, be stable peroxyacetic acid disinfectant.
Peroxyacetic acid disinfectant of the present invention has following technological merit and characteristics:
1. primary raw material of the present invention adopts common hydrogen peroxide and acetate to produce; can improve Peracetic acid concentration though adopt acetic anhydride to replace acetate to make raw material; but in generative process, can produce explosive accessory substance diacyl peroxide; production process is on the rack entirely; and require complicated production technology and security measure, cause the production cost height.
2. Peracetic acid character instability is met metal impurities meeting accelerated decomposition in the storage process, can blast when sharply decomposing.And the trace meter that influences Stability of Acetic acid peroxide is mainly: Fe, Co, Cu, Ni, Mn, the present invention add the compound stabilizer of being made up of tungstates or molybdate, organic phosphorus compound, benzenetricarboxylic acid.Not only can play the effect of stablizing the Peracetic acid reaction system, and the trace metal ion in can also complex solution, slow down the decomposition of Peracetic acid.Thereby make peroxyacetic acid disinfectant stability and security more.
Six valence electrons of molybdenum (4d55s1) and tungsten (5d46s2) can be participated in into the key effect, and highest oxidation state is+VI, and have multiple oxidation state.The solution and the another kind of oxyacid soln that will contain molybdate (or tungstates) mixes, acidifying, can make the heteropolyacid salt of molybdenum (or tungsten).Molybdate and tungstates good stability, low toxicity, nuisanceless.
Organic phosphorus compound have can be for the P atom that utilizes lone pair electrons, and with tungstates or molybdate acting in conjunction, but the part trace meter in the complex solution (Fe, Co, Ni etc.) forms tungsten phospha multi-acid salt or molybdenum phospha multi-acid salt.
Benzenetricarboxylic acid (H
3BTC) can have the complex of two-dimensional network structure with formation such as metal ion Cu and Mn.Each manganese ion and two H
3BTC ion and four hydrone coordinations form [Mn (H
3BTC)
2(H
2O)
4] .2H
2O; Each copper ion and three H
3BTC and two sub-coordinations of moisture content form [Cu (H
3BTC)
3(H
2O)
2] .2H
2O.The existence of carboxyl simultaneously can be worked in coordination with the reaction system of stablizing Peracetic acid.
3. add surfactant such as isomery alcohol ether non-ionic surface active agent in peroxyacetic acid disinfectant of the present invention, belong to low bubble non-ionic surface active agent, its characteristics are that foam is low, and easily biological-degradable is acidproof, resistance to oxidation.The adding of such surfactant can improve the wetability of peroxyacetic acid disinfectant, promotes disinfectant and surperficial contacting, and improves Disinfection Effect.
In addition, peroxyacetic acid disinfectant of the present invention, its Peracetic acid concentration can be regulated by the increase and decrease of hydrogen peroxide and acetic acid raw material consumption, satisfies the needs of variable concentrations.
Characteristics such as peroxyacetic acid disinfectant of the present invention has Peracetic acid concentration height, good stability, sterilization effect is good and production technology simple, safety.
[description of drawings]
Fig. 1 is the comparison diagram of the stability of two kinds of production method Peracetic acid;
Fig. 2 is the comparison diagram of the stability of Peracetic acid.
[embodiment]
Preparation embodiment one
1. take by weighing sodium tungstate 25g, ethylenediamine tetraacetic methyl acid phosphate 25g, 1,3 respectively, 5-1,3,5-Benzenetricarboxylic acid 50g mixes and fully stirs obtaining the 100g compound stabilizer.
2. take by weighing compound stabilizer, 100g isomery ten pure polyoxyethylene ether surface active agents, 3400g hydrogen peroxide, 3000g acetate and the 3400g water of the above-mentioned preparation of 100g respectively.
3. earlier water is pumped in the enamel jacket reactor, add compound stabilizer and surfactant and stirring and dissolving then, pump into hydrogen peroxide, acetate more successively, stirred 30 minutes, promptly obtain stable peroxyacetic acid disinfectant.
Preparation embodiment two
1. take by weighing potassium tungstate 25g, hydroxy-methylbenzene fork diphosphonic acid 25g, 1,2 respectively, 3-benzene-1 50g mixes and fully stirs obtaining the 100g compound stabilizer.
2. take by weighing compound stabilizer, 100g isomery undecyl alcohol polyoxyethylene ether surface active agent, 3400g hydrogen peroxide, 3000g acetate and the 3400g water of the above-mentioned preparation of 100g respectively.
3. earlier water is pumped in the enamel jacket reactor, add compound stabilizer and surfactant and stirring and dissolving then, pump into hydrogen peroxide, acetate more successively, stirred 30 minutes, promptly obtain stable peroxyacetic acid disinfectant.
Ratio embodiment one: the synthetic Peracetic acid of typical method with do not add the comparison of the stability of the synthetic Peracetic acid of catalyzer (sulfuric acid):
1. typical method is synthetic: hydrogen peroxide and acetate react in the presence of sulfuric acid catalyst
2. it is synthetic not add catalyzer: hydrogen peroxide and acetate directly react
Both are after the room temperature lucifuge is stored, and through 12 calendar months, outward appearance is as clear as crystal, and no change color and not having precipitates and suspension.Its Peracetic acid content more as shown in Figure 1:
Because the catalytic action of sulfuric acid, the aggregate velocity of Peracetic acid just can record its maximum concentration than very fast after 48 hours from the synthetic Peracetic acid of the visible typical method of Fig. 1; And when not adding catalyzer, the aggregate velocity of Peracetic acid is relatively slow, just records its maximum concentration after 144 hours.Because the both do not add other stabilizing agents, the degraded of Peracetic acid is also than comparatively fast, and its degradation rate has all surpassed 50% after 60 days.
Ratio embodiment two: do not add the comparison of the stability of the synthetic Peracetic acid of the stabilizing agent Peracetic acid synthetic with adding compound stabilizer
1. it is synthetic not add the stabilizing agent agent: hydrogen peroxide and acetate directly react
2. it is synthetic to add compound stabilizer: hydrogen peroxide and acetate reaction in the presence of the compound stabilizer both after the storage of room temperature lucifuge, through 12 calendar months, outward appearance is as clear as crystal, no change color and not having precipitates and suspension.Its Peracetic acid content more as shown in Figure 2:
As seen add the stable fine of the synthetic Peracetic acid of compound stabilizer from Fig. 2, can remain on stable state always in 1 year, the rate of descent of Peracetic acid content is no more than 5%.And the degraded of Peracetic acid of not adding stabilizing agent is very fast, and its degradation rate has surpassed 70% after 100 days.
Ratio embodiment three: the comparison of the peracetic acid disinfectant bactericidal effect that Peracetic acid that typical method is synthetic and interpolation compound stabilizer are synthetic
1. the synthetic Peracetic acid (DPAA) of typical method: hydrogen peroxide and acetate react in the presence of sulfuric acid catalyst, and Peracetic acid concentration is 19.99% during use.
2. add the synthetic Peracetic acid (WPAA) of compound stabilizer: hydrogen peroxide and acetate react in the presence of compound stabilizer, and Peracetic acid concentration is 20.13% during use.
Sterilization effect is shown in table 1-4.
The different peracetic acid disinfectant liquid of table 1 are to colibacillary killing effect
Annotate: average positive control bacterium several 3.18 * 10
8Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 2 are to the killing effect of staphylococcus aureus
Annotate: positive control bacterium several 2.45 * 10
8Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 3 are to the killing effect of black-koji mould
Annotate: average positive control bacterium several 1.31 * 10
7Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 4 are to the killing effect of bacillus subtilis black variety gemma
Annotate: average positive control bacterium several 2.67 * 10
7Cfu/ml, test temperature is 25 ℃, test repeats 3 times
As seen add the dissipation effect no significant difference of the Peracetic acid that the synthetic Peracetic acid of compound stabilizer and typical method synthesize by table 1-4.
Ratio embodiment four: add the comparison of the synthetic Peracetic acid of the compound stabilizer Peracetic acid dissipation effect synthetic with adding compound stabilizer and surfactant
1. add the synthetic Peracetic acid (WPAA) of compound stabilizer: hydrogen peroxide and acetate react in the presence of compound stabilizer, and Peracetic acid concentration is 20.13% during use.
2. add the synthetic Peracetic acid (FPAA) of compound stabilizer and surfactant: hydrogen peroxide and acetate react in the presence of compound stabilizer and surfactant, and Peracetic acid concentration is 19.87% during use.
Sterilization effect is shown in table 1-4.
The different peracetic acid disinfectant liquid of table 5 are to colibacillary killing effect
Annotate: average positive control bacterium several 3.18 * 10
8Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 6 are to the killing effect of staphylococcus aureus
Annotate: positive control bacterium several 2.45 * 10
8Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 7 are to the killing effect of black-koji mould
Annotate: average positive control bacterium several 1.31 * 10
7Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The different peracetic acid disinfectant liquid of table 8 are to the killing effect of bacillus subtilis black variety gemma
Annotate: average positive control bacterium several 2.67 * 10
7Cfu/ml, test temperature is 25 ℃, test repeats 3 times
The dissipation effect of as seen adding the synthetic Peracetic acid (FPAA) of compound stabilizer and surfactant by table 5-8 slightly is better than only adds the synthetic Peracetic acid (WPAA) of compound stabilizer.
Claims (8)
1. stable peroxyacetic acid disinfectant, it is characterized in that each raw material mass percent is: hydrogen peroxide: 27-39%, acetate: 22-36%, compound stabilizer: 0.01-2%, surfactant: 0.01-2%, all the other are water, the mass concentration of Peracetic acid is 15-20g/100g in the prepared peroxyacetic acid disinfectant, and hydrogen peroxide is that 20-30g/100g, acetate are 10-20g/100g.
2. peroxyacetic acid disinfectant as claimed in claim 1, it is characterized in that each raw material mass percent is: hydrogen peroxide: acetate 34%: compound stabilizer 30%: surfactant 1%: 1%, all the other are water, and the mass concentration of Peracetic acid is 20g/100g in the prepared peroxyacetic acid disinfectant.
3. peroxyacetic acid disinfectant as claimed in claim 1 or 2 is characterized in that described compound stabilizer is made up of tungstates or molybdate, organic phosphorus compound, benzenetricarboxylic acid, and its weight ratio is 1:1:2.
4. tungstates as claimed in claim 3 can be a kind of in sodium tungstate, potassium tungstate, tungstate lithium and the wolframic acid amine etc.
5. molybdate as claimed in claim 3 can be a kind of in sodium molybdate, potassium molybdate, lithium molybdate and the amine molybdate etc.
6. organic phosphorus compound as claimed in claim 3 can be a kind of in ethylenediamine tetraacetic methyl acid phosphate, hydroxy-methylbenzene fork diphosphonic acid, hydroxyl ethane fork diphosphonic acid, diethylenetriamine five methene phosphoric acid, the dimethylamino methane fork diphosphonic acid etc.
7. benzenetricarboxylic acid as claimed in claim 3 can be 1,2,3-benzene-1,1,3,5-1,3,5-Benzenetricarboxylic acid, 1,2, a kind of in the 4-trimellitic acid etc.
8. surfactant as claimed in claim 1 or 2 can be a kind of in the isomery alcohol ether non-ionic surface active agents such as isomery ten pure APEOs, isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether.
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| CN108260590A (en) * | 2018-03-13 | 2018-07-10 | 陕西康禾立丰生物科技药业有限公司 | A kind of bactericidal composition containing Peracetic acid |
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| CN113801028A (en) * | 2021-10-15 | 2021-12-17 | 成都科宏达科技有限公司 | Special surfactant for hydrogen peroxide and compound thereof |
| CN113801028B (en) * | 2021-10-15 | 2023-11-10 | 成都科宏达科技有限公司 | Special surfactant for hydrogen peroxide and compound thereof |
| CN114698634A (en) * | 2022-03-09 | 2022-07-05 | 四川科宏达集团有限责任公司 | Application of isomeric tridecanol polyoxyethylene ether in iodine disinfectant and application method thereof |
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