CN105746512A - Quaternary ammonium salt type water treatment bactericide - Google Patents
Quaternary ammonium salt type water treatment bactericide Download PDFInfo
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- CN105746512A CN105746512A CN201610129785.1A CN201610129785A CN105746512A CN 105746512 A CN105746512 A CN 105746512A CN 201610129785 A CN201610129785 A CN 201610129785A CN 105746512 A CN105746512 A CN 105746512A
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- Prior art keywords
- quaternary ammonium
- ammonium salt
- water treatment
- salt water
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Abstract
The invention discloses a quaternary ammonium salt type water treatment bactericide.The bactericide is mainly prepared from, by weight, 10-30 parts of mono-quaternary ammonium salt, 20-30 parts of poly-quaternary ammonium salt, 15-20 parts of polyaspartic acid, 5-15 parts of polymaleic anhydride, 5-15 parts of metal salt and 30-60 parts of deionized water.The quaternary ammonium salt type water treatment bactericide has the advantages of high efficiency, low toxicity, insusceptibility to pH value variation, convenience in use, strong stripping effect on slime layers, chemical stability and excellent dispersion and corrosion inhibition performances.
Description
Technical field
The present invention relates to environment-protective water process field, particularly a kind of quaternary ammonium salt water treatment biocide.
Background technology
Bactericide conventional in industry is divided into two big classes, oxidized form and non-oxidative bactericide.Conventional oxygen
Change type bactericide mainly includes that chlorine, sodium dichloro cyanurate (are called for short Puritabs, trichlorine isocyanide urine
Acid (abbreviation strong chlorine oil) etc.；Conventional non-oxidative bactericide mainly includes quaternary ammonium salt.Organic matter,
Quaternary salt type organic, OIT, glutaraldehyde etc..Oxidative bactericide is because it is cheap
Be commonly used, but its easily affected by pH, organic matter, anti-incrustation corrosion inhibitor etc. in recirculated cooling water and
Interference, is allowed to bactericidal effect and reduces, and Long-Time Service, owing to microorganism impact of developing immunity to drugs is killed
Bacterium effect；Non-oxidative bactericide does not kills microorganism in water with oxidation, but by acting on
The privileged sites of microorganism are allowed to lethal, therefore, non-oxidative bactericide not by pH in recirculated cooling water,
The impact of the factor such as organic matter, anti-incrustation corrosion inhibitor and interference.Non-oxidative bactericide is also used as oxygen
The aid antibacteria agent of change type bactericide, periodically uses in recirculated cooling water, can cool down with strip cycles
Biological sludge in industrial in water system, can prevent microorganism from developing immunity to drugs simultaneously.The compounding of bactericide is to solve
Determine microbial resistance and make medicament multifunction (when referring to that stripping, instantaneous sterilization effect and sterilization continue
Between the function such as long) a kind of effective ways.A kind of water as disclosed in Publication No. CN104430501A
Process bromine series bactericidal agent and preparation method thereof, solve existing water and process that anti-microbial agents sterilizing rate is low, sterilization
The technical problems such as slow and easy environmental pollution, but it is sufficiently complex to fill a prescription.
Compounding between compounding generally non-oxidative bactericide.Principle of compound is two or more sterilizations
After agent is compounding, the bactericidal property of compound disinfectant is better than each bactericide independent role sum.Require becoming
Decrease on Ben, performance has collaborative or complementary effect.Up to the present, compound disinfectant is equal
Only there is sludge stripping and bactericidal property, do not possess corrosion-mitigation scale-inhibition function, such as publication number
The technical scheme of a kind of Treatment of Industrial Water bactericide disclosed in CN105104387 with the addition of again dichloro
Sodium isocyanurate sterilization and antisludging agent.To this end, when reality is applied must by the bactericide after compound with
Other corrosion inhibiting and descaling agents are properly functioning with the use of guarantee recirculated water.
Summary of the invention
The invention aims to overcome the deficiencies in the prior art, it is provided that a kind of quaternary ammonium salt water processes
Bactericide, described bactericide has efficiently, low toxicity, be susceptible to pH value change impact, user
Just, to slime layer have stronger release effect, a stable chemical performance, and dispersion and corrosion inhibition preferable.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of quaternary ammonium salt water treatment biocide, described bactericide is mainly by following one-tenth
Divide and form by weight: mono-quaternaries 10～30 parts, polyquaternium 20～30 parts, poly-aspartate 15～20
Part, HPMA 5～15, slaine 5-15 part, deionized water 30～60 parts；
Described mono-quaternaries is dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl chlorine
Change ammonium, DTAC, chlorine double octyldimethyl ammonium, didecyl Dimethy chlorination
One in ammonium, preferably didecyl Dimethy ammonium chloride；Quaternary ammonium salt cationic passes through electrostatic force, hydrogen
The effects such as the hydrophobic binding between bonding force and surfactant molecule and protein molecule, adsorb electronegative
Bacterial body, be gathered on cell membrane, generating chamber's inhibition effect, cause bacterial growth suppressed and dead；
Its hydrophobic alkyl with the hydrophilic group effect of bacterium, can also change the permeability of film simultaneously, then occurs molten
Born of the same parents act on, and destroy eucaryotic cell structure, cause dissolving and the death of cell, and quaternary ammonium salt has extremely strong thickening
Ability, good wetting, disperse, emulsify, inhibition and sterilizing ability；
Described polyquaternium be chlorination-2-hydroxyl-3-(dimethylamino) propyl group PEO cellulose ether,
N, N, N-trimethyl-2-[(2-methyl isophthalic acid-oxygen-2-acrylic) epoxide] ethylamine hydrochloride, dimethyl diene
In propyl ammonium chloride-acrylic copolymer, dimethyl diallyl ammonium chloride-acrylamide copolymer
A kind of；Polyquaternium bactericide belongs to strong cation high molecular polymer, has good dissolubility in water
Can, there is wide spectrum, efficient sterilization algae removal ability, bacterium algae propagation and foundry loam in water can be efficiently controlled
Growth, and there is good sludge stripping effect and certain dispersion, osmosis, have one simultaneously
Fixed deoil, deodorizing capability and corrosion inhibition；
Described slaine is the one in magnesium nitrate, magnesium chloride, zinc sulfate, ferric sulfate；Described sterilization
Agent composition also includes that dispersant, described dispersant are acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymerization
One in thing, acrylic acid-allyloxy polyether-acrylic acid esters co-polymer；The addition of dispersant,
Reduce the time used by dispersion process and energy, prevent flocculation, prevent precipitation, and dispersant itself
Do not affect the performance of bactericide, nontoxic, with low cost；
Described bactericide composition also includes that polymerization inhibitor, described polymerization inhibitor are hydroxyanisol, diisooctyl
Diphenylamines, butyl diphenylamines；The addition of polymerization inhibitor can effectively stop self or mutual polymerization anti-
Should；Described inorganic acid is the one in hydrochloric acid, phosphoric acid or sulfuric acid；
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) mono-quaternaries, polyquaternium, poly-aspartate, poly-Malaysia are weighed respectively by formula ratio
Acid anhydrides, slaine, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 10～30 minutes, make HPMA be fully hydrolyzed at normal temperatures, then
Add poly-aspartate, continue to stir；
(3) slaine is joined in reactor, stir stirring in 20～40 minutes under normal temperature and be allowed to fill
Divide and dissolve；
(4) stir 20～30 minutes after the last polyquaternium of addition in the reactor, add single cropping
Ammonium salt stirs, and obtains product.
One quaternary ammonium salt water treatment biocide of the present invention, has a following beneficial effect:
The first, quaternary ammonium salt cationic is by electrostatic force, hydrogen bond force and surfactant molecule and albumen
The intermolecular hydrophobic bindings of matter etc. act on, and adsorb electronegative bacterial body, are gathered on cell membrane, produce
Raw room inhibition effect, causes bacterial growth suppressed and dead；Its hydrophobic alkyl can also be with the parent of bacterium simultaneously
Water base effect, changes the permeability of film, and lysis occurs then, destroys eucaryotic cell structure, causes thin
The dissolving of born of the same parents and death, have extremely strong tackifying ability, good wetting, disperse, emulsify, inhibition
And sterilizing ability.
The second, polyquaternium bactericide belongs to strong cation high molecular polymer, has the most molten in water
Solve performance, there is wide spectrum, efficient sterilization algae removal ability, can efficiently control in water bacterium algae propagation and
Foundry loam grows, and has good sludge stripping effect and certain dispersion, osmosis, has simultaneously
Have certain deoil, deodorizing capability and corrosion inhibition
3rd, bactericide of the present invention uses and quaternary ammonium salt and polyquaternium is compounded, compound disinfectant
Bactericidal property be better than each bactericide independent role sum, played each to greatest extent by Synergistic
The potentiality of component, performance have collaborative or complementary effect, and the most additionally add antisludging agent and inhibition
Agent, meets the requirement of industry water microbial diversity sterilization processing.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, below in conjunction with reality
Execute example technical scheme is described in further detail.
Embodiment 1
Formula: quaternary ammonium salt water treatment biocide, is mainly made up of following component: 12 by weight
Zephiran 12 parts, N, N, N-trimethyl-2-[(2-methyl isophthalic acid-oxygen-2-acrylic)
Epoxide] ethylamine hydrochloride 20～30 parts, poly-aspartate 16 parts, HPMA 12, ferric sulfate 10
Part, deionized water 50 parts.
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) dodecyl benzyl dimethyl ammonium chloride, N, N, N-trimethyl are weighed respectively by formula ratio
-2-[(2-methyl isophthalic acid-oxygen-2-acrylic) epoxide] ethylamine hydrochloride, poly-aspartate, HPMA,
Ferric sulfate, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 15 minutes, make HPMA be fully hydrolyzed, then add at normal temperatures
Enter poly-aspartate, continue to stir；
(3) ferric sulfate is joined in reactor, stir stirring in 25 minutes under normal temperature and be allowed to the most molten
Solve；
(4) finally N, N, N-trimethyl-2-[(2-methyl isophthalic acid-oxygen-2-acrylic) are added in the reactor
Epoxide] stir 20 minutes after ethylamine hydrochloride, add dodecyl benzyl dimethyl ammonium chloride abundant
Stir, obtain product.
Embodiment 2
Formula: quaternary ammonium salt water treatment biocide, is mainly made up of following component: 14 by weight
Zephiran 15 parts, dimethyl diallyl ammonium chloride-acrylic copolymer 20 parts,
Poly-aspartate 18 parts, HPMA 12,13 parts of magnesium chloride, deionized water 45 parts.
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) myristyl benzyl dimethyl ammonium chloride, dimethyl two allyl is weighed respectively by formula ratio
Ammonium chloride-acrylic copolymer, poly-aspartate, HPMA, magnesium chloride, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 20 minutes, make HPMA be fully hydrolyzed, then add at normal temperatures
Enter poly-aspartate, continue to stir；
(3) magnesium chloride is joined in reactor, stir stirring in 30 minutes under normal temperature and be allowed to the most molten
Solve；
(4) stir after finally adding dimethyl diallyl ammonium chloride-acrylic copolymer in the reactor
Mix 25 minutes, add myristyl benzyl dimethyl ammonium chloride and stir, obtain product.
Embodiment 3
Formula: quaternary ammonium salt water treatment biocide, is mainly made up of following component: double ten by weight
Alkyl dimethyl ammonium chloride 28 parts, chlorination-2-hydroxyl-3-(dimethylamino) propyl group PEO are fine
Dimension element 30 parts of ether, poly-aspartate 16 parts, HPMA 9,10 parts of zinc sulfate, deionized water
40 parts.
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) didecyl Dimethy ammonium chloride, chlorination-2-hydroxyl-3-(three is weighed respectively by formula ratio
Methylamino) propyl group PEO cellulose ether, poly-aspartate, HPMA, zinc sulfate,
Deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 20 minutes, make HPMA be fully hydrolyzed, then add at normal temperatures
Enter poly-aspartate, continue to stir；
(3) zinc sulfate is joined in reactor, stir stirring in 30 minutes under normal temperature and be allowed to the most molten
Solve；
(4) finally chlorination-2-hydroxyl-3-(dimethylamino) propyl group polycyclic oxygen second is added in the reactor
Stir 30 minutes after alkoxy cellulose ether, add didecyl Dimethy ammonium chloride and stir,
Obtain product.
Embodiment 4
Formula: quaternary ammonium salt water treatment biocide, is mainly made up of following component: double ten by weight
Alkyl dimethyl ammonium chloride 26 parts, dimethyl diallyl ammonium chloride-acrylic copolymer 25 parts, poly-
Aspartic acid 16 parts, HPMA 12, magnesium nitrate 15 parts, deionized water 55 parts.
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) didecyl Dimethy ammonium chloride, dimethyl diallyl chlorine are weighed respectively by formula ratio
Change ammonium-acrylic copolymer, poly-aspartate, HPMA, magnesium nitrate, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 15 minutes, make HPMA be fully hydrolyzed, then add at normal temperatures
Enter poly-aspartate, continue to stir；
(3) magnesium nitrate is joined in reactor, stir stirring in 20 minutes under normal temperature and be allowed to the most molten
Solve；
(4) stir after finally adding dimethyl diallyl ammonium chloride-acrylic copolymer in the reactor
Mix 25 minutes, add didecyl Dimethy ammonium chloride and stir, obtain product.
Embodiment 5
Formula: quaternary ammonium salt water treatment biocide, is mainly made up of following component: 14 by weight
Zephiran 19 parts, dimethyl diallyl ammonium chloride-acrylamide 26 parts, poly-
Aspartic acid 17 parts, HPMA 12,10 parts of zinc sulfate, deionized water 40 parts.
The preparation method of described quaternary ammonium salt water treatment biocide, comprises the steps:
(1) myristyl benzyl dimethyl ammonium chloride, dimethyl two allyl is weighed respectively by formula ratio
Ammonium chloride-acrylamide, poly-aspartate, HPMA, zinc sulfate, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined reactor
In, hydrolyzing and stir, stirring 20 minutes, make HPMA be fully hydrolyzed, then add at normal temperatures
Enter poly-aspartate, continue to stir；
(3) zinc sulfate is joined in reactor, stir stirring in 25 minutes under normal temperature and be allowed to the most molten
Solve；
(4) 30 are stirred after finally adding dimethyl diallyl ammonium chloride-acrylamide in the reactor
Minute, add myristyl benzyl dimethyl ammonium chloride and stir, obtain product.
In order to assess the concrete effect of a kind of quaternary ammonium salt water treatment biocide product of the present invention, point
The bactericide of embodiment 1～5 is placed one month, sterilizing rate after half a year, 2 years specifically surveys
Examination, adds 20mg/L, is sterilized iron bacteria and sulfate reducing bacteria, and result is as shown in table 1:
The bactericidal effect of table 1 embodiment 1～5 gained bactericide
As it can be seen from table 1 the bactericide of the present invention has the bactericidal property of excellence, and when long
Between place after sterilizing rate is the most significantly affected.
The above, only presently preferred embodiments of the present invention, not the present invention is made any form
On restriction；The those of ordinary skill of all industry all can shown in by specification and the above and smooth and easy
The present invention is implemented on ground；But, all those skilled in the art are without departing from technical solution of the present invention
In the range of, available disclosed above technology contents and make a little change, modify and develop
Equivalent variations, is the Equivalent embodiments of the present invention；Meanwhile, all substantial technological pair according to the present invention
The change of any equivalent variations that above example is made, modify and differentiation etc., all still fall within the present invention
Technical scheme protection domain within.
Claims (10)
1. a quaternary ammonium salt water treatment biocide, it is characterised in that described bactericide is main
It is made up of by weight following component: mono-quaternaries 10～30 parts, polyquaternium 20～30 parts,
Poly-aspartate 15～20 parts, HPMA 5～15, slaine 5-15 part, deionized water
30～60 parts.
A kind of quaternary ammonium salt water treatment biocide the most according to claim 1, its feature
Being, described mono-quaternaries is dodecyl benzyl dimethyl ammonium chloride, dodecyldimethylamine base
Benzyl ammonium chloride, DTAC, chlorine double octyldimethyl ammonium, double ten alkyl
One in alkyl dimethyl ammonium chloride.
A kind of quaternary ammonium salt water treatment biocide the most according to claim 1, its feature
Being, described polyquaternium is chlorination-2-hydroxyl-3-(dimethylamino) propyl group PEO
Cellulose ether, N, N, N-trimethyl-2-[(2-methyl isophthalic acid-oxygen-2-acrylic) epoxide] ethamine hydrochloric acid
Salt, dimethyl diallyl ammonium chloride-acrylic copolymer, dimethyl diallyl ammonium chloride-
One in acrylamide copolymer.
4. according to a kind of quaternary ammonium salt water treatment biocide described in claim 1 or 2 or 3,
It is characterized in that, described slaine is in magnesium nitrate, magnesium chloride, zinc sulfate, ferric sulfate
Kind.
A kind of quaternary ammonium salt water treatment biocide the most according to claim 1, its feature
Being, described bactericide composition also includes that dispersant, described dispersant are acrylic acid-2-acryloyls
In amine-2-methyl propane sulfonic acid copolymer, acrylic acid-allyloxy polyether-acrylic acid esters co-polymer
One.
A kind of quaternary ammonium salt water treatment biocide the most according to claim 1, its feature
Be, described bactericide composition also include polymerization inhibitor, described polymerization inhibitor be hydroxyanisol, two
One in di-iso-octyldiphenylamine, butyl diphenylamines.
The preparation side of a kind of quaternary ammonium salt water treatment biocide the most according to claim 1
Method, comprises the steps:
(1) weigh mono-quaternaries, polyquaternium, poly-aspartate by formula ratio respectively, gather
Maleic anhydride, slaine, deionized water；
(2) deionized water is joined in reactor, then HPMA is joined instead
Answer in device, hydrolyze and stir, adding poly-aspartate, continue to stir；
(3) joining in reactor by slaine, stirring is allowed to fully dissolve；
(4) the last polyquaternium that adds in the reactor stirs, and adds mono-quaternaries abundant
Stir, obtain product.
The preparation side of a kind of quaternary ammonium salt water treatment biocide the most according to claim 7
Method, it is characterised in that described step (2) stirs 10～30 minutes at normal temperatures, makes poly-horse
Carry out acid anhydrides to be fully hydrolyzed.
The preparation side of a kind of quaternary ammonium salt water treatment biocide the most according to claim 7
Method, it is characterised in that stir 20～40 under normal temperature after adding slaine in described step (3)
Minute.
10. process sterilization according to a kind of quaternary ammonium salt water described in claim 7～9 any one
The preparation method of agent, it is characterised in that stir after adding polyquaternium in described step (4)
20～30 minutes, add and after quaternary ammonium salt is sufficiently stirred for, i.e. obtain quaternary ammonium salt water treatment biocide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610129785.1A CN105746512A (en) | 2016-03-08 | 2016-03-08 | Quaternary ammonium salt type water treatment bactericide |
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| CN201610129785.1A CN105746512A (en) | 2016-03-08 | 2016-03-08 | Quaternary ammonium salt type water treatment bactericide |
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| CN108329411A (en) * | 2018-04-27 | 2018-07-27 | 南京大学 | A kind of composite function resin and preparation method and application |
| CN108926494A (en) * | 2018-06-26 | 2018-12-04 | 苏州美瑞姿生物科技有限公司 | Poly-aspartate sodium salt combination solution and preparation method thereof, application |
| CN109258672A (en) * | 2018-10-31 | 2019-01-25 | 福州盛世凌云环保科技有限公司 | A kind of high efficiency composition benomyl Biocidal algae-killing agent and preparation method thereof |
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| CN112830558A (en) * | 2020-12-31 | 2021-05-25 | 江西省水利科学研究院 | Selectively-killing-deactivated blue algae-removing modified soil and preparation method thereof |
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| CN106345261A (en) * | 2016-08-23 | 2017-01-25 | 南京南炼宏泰技术开发有限公司 | Environmental-friendly high-efficacy deodorant and method for preparing same |
| CN108329411A (en) * | 2018-04-27 | 2018-07-27 | 南京大学 | A kind of composite function resin and preparation method and application |
| CN108329411B (en) * | 2018-04-27 | 2019-11-22 | 南京大学 | A kind of composite function resin and preparation method and application |
| CN108926494A (en) * | 2018-06-26 | 2018-12-04 | 苏州美瑞姿生物科技有限公司 | Poly-aspartate sodium salt combination solution and preparation method thereof, application |
| CN109258672A (en) * | 2018-10-31 | 2019-01-25 | 福州盛世凌云环保科技有限公司 | A kind of high efficiency composition benomyl Biocidal algae-killing agent and preparation method thereof |
| CN109258668A (en) * | 2018-10-31 | 2019-01-25 | 福州盛世凌云环保科技有限公司 | A kind of high efficiency composition carbendazim Biocidal algae-killing agent and preparation method thereof |
| CN111068633A (en) * | 2020-01-31 | 2020-04-28 | 广州绿邦环境技术有限公司 | Organic water purifying agent and production process thereof |
| CN112830558A (en) * | 2020-12-31 | 2021-05-25 | 江西省水利科学研究院 | Selectively-killing-deactivated blue algae-removing modified soil and preparation method thereof |
| CN114652741A (en) * | 2022-01-19 | 2022-06-24 | 昆明野水生物科技有限公司 | Composition and preparation for inhibiting HPV and application thereof |
| CN114652741B (en) * | 2022-01-19 | 2023-08-25 | 昆明野水生物科技有限公司 | Composition and preparation for inhibiting HPV and application of composition and preparation |
| CN115448432A (en) * | 2022-11-11 | 2022-12-09 | 山东海化集团有限公司 | Sterilization and decontamination agent in brine system and preparation method thereof |
| CN115448432B (en) * | 2022-11-11 | 2023-04-07 | 山东海化集团有限公司 | Sterilization stain remover in brine system and preparation method thereof |
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Application publication date: 20160713 |