CN104488957A - Efficient composite germicide for circulating water system and preparation method thereof - Google Patents
Efficient composite germicide for circulating water system and preparation method thereof Download PDFInfo
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- CN104488957A CN104488957A CN201410753286.0A CN201410753286A CN104488957A CN 104488957 A CN104488957 A CN 104488957A CN 201410753286 A CN201410753286 A CN 201410753286A CN 104488957 A CN104488957 A CN 104488957A
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Abstract
The invention discloses an efficient composite germicide for a circulating water system, which is composed of the following components: 15-18% of glutaraldehyde, 42-49% of quaternary phosphonium, 11-17% of isothiazolinone, 20-30% of deionized water, and 5-8% of dithiocyano-methane. The germicide has an extremely excellent bactericidal effect, can be used in circulating cooling water under high pH value conditions, has a good killing effect on heterotrophic bacteria, sulfate reducing bacteria and algae, and especially has an obvious killing effect on heterotrophic bacteria; and the germicide is high in killing speed, strong in killing force, and low in toxicity.
Description
Technical field
The invention belongs to industrial circulation water treatment technical field, relate to a kind of high efficiency composition bactericide and preparation method thereof.
Background technology
Bactericide is a kind of very common water treatment agent, is mainly used in recirculating cooling water system.Because recirculating cooling water system has special ecotope, microorganism easily inside amount reproduction, the amount reproduction of microorganism also can produce a large amount of microorganism viscosity muds in circulation simultaneously.The foundry loam produced when the amount reproduction of microorganism and breeding can make cooling water quality sharply worsen; simultaneously; the glutinous mud formed is deposited in cooling tower and heat transmission equipment; completely cut off the protective effect of medicament to metal; make medicament can not play due corrosion-mitigation scale-inhibition usefulness; and the hardware in cooling water system can be caused to corrode; also can blocking pipe time serious; directly enterprise security is normally produced and cause threat; in order to avoid the generation of this kind of situation, the most directly way is exactly the breeding adding microorganism in bactericide control system.
Conventional bactericide can be divided into oxidisability and the large class of non oxidizing bactericide two.The bactericide of one-component has that dosage is large, kind is single, easily develops immunity to drugs and the shortcomings such as fragmentation effect difference.And there is the compound prescription of synergistic effects, one-component relatively wherein has synergistic effect, and can overcome the weakness of killing livestock of one-component, can also reduce costs.It is composite that to be generally between non oxidizing bactericide composite, principle of compound be two or more bactericide compounded after, the combination property of compound disinfectant is better than each bactericide and is used alone, and performance has coordination or complementary effect.
The CN102726446A applied for before the applicant discloses a kind of circulation high efficiency composition bactericide, and described high efficiency composition material of germicide component and percentage by weight are: glutaraldehyde 20%-30%, quaternary alkylphosphonium salt 30%-40%, isothiazolinone 10%-20%, deionized water 20%-30%; Wherein said quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium or tetrakis hydroxymethyl phosphonium chloride or tributyltetradecylphchloridem chloridem, the optional one of three.The active component that CN101578997A discloses a kind of compound disinfectant is made up of following a few class non oxidizing bactericide: tribenzyl phenyl phosphonium chloride (A), dithiocyano-methane (B), copper sulphate (C), the weight ratio of A, B and C of recommendation is 10 ~ 20: 10 ~ 35: 1.Patent of invention CN1853468A discloses a kind of composite efficient aldehyde insecticide, and it is made up of glutaraldehyde 20%-40%, quaternary ammonium salt 20%-40%, auxiliary agent 5%-20%.The quaternary ammonium salt selected in its patent can not share with chlorophenols biocide, should not share, there is Ca in a large number in cycle water with anion surfactant
2+, Mg
2+, Al
3+and Fe
2+during metal ion, can reduce the effect of killing livestock of quaternary ammonium salt, Long-Time Service easily makes microorganism develop immunity to drugs, and adding consistency rises, and water treatment expense increases, and quaternary ammonium salt foam easy to foaming, together need use with defoamer, be unfavorable for industrial production, easily cause environmental pollution.
Summary of the invention
For the above-mentioned problems in the prior art, the object of this invention is to provide a kind of circulation high efficiency composition bactericide, in cycle water, there is Ca to solve prior art products in a large number
2+, Mg
2+, Al
3+and Fe
2+during metal ion, the effect of killing livestock of quaternary ammonium salt reduces, can not share with chlorophenols biocide, should not share with anion surfactant, Long-Time Service easily makes microorganism develop immunity to drugs, adding consistency rises, water treatment expense increases, and easy to foaming, and normal and defoamer together uses, be unfavorable for industrial production, easily cause the problems such as environmental pollution.Invention also provides the production method that it is simple.
The technical solution adopted for the present invention to solve the technical problems the quaternary ammonium salt of foam easy to foaming is replaced by the not easy to foaming and environment-friendly type quaternary alkylphosphonium salt of easily biological-degradable.
Quaternary alkylphosphonium salt is a kind of biocide of wide spectrum, its molecular structure is similar to quaternary ammonium salt, just replace nitrogenous cation quaternary alkylphosphonium salt in quaternary ammonium salt positively charged after ionizing in water with phosphorous cation, electronegative antimicrobial surface can be adsorbed on and penetrate into inside microbes, change the character of primary film, make bacterium can not normal activity; Hydrophobic group makes the fatty wall on bacterial body surface dissolve, thus causes bacterial death.The feature of its existing quaternary ammonium salt biocide wide spectrum of similar structures shape, efficient and quick sterilization, again without the shortcoming ， quaternary alkylphosphonium salt becoming bubble and react with anionic medicament to Gram-negative bacteria, gram-positive bacteria and mould and algae etc. effectively.In addition to generation H
2the sulfate reducing bacteria one class anaerobic bacteria of S is especially effective; Its great advantage is low to fish toxicity, can degrade rapidly to innocuous substance rapidly, do not have cumulative toxicity effect after using by hydrolysis, oxidation, light degradation and biodegradable mode.
High efficiency composition material of germicide of the present invention is composed of the following components: glutaraldehyde 15%-18%, quaternary alkylphosphonium salt 42%-49%, isothiazolinone 11%-17%, deionized water 20%-30%, dithiocyano-methane 5-8%.
Said components is weight percentage;
Quaternary alkylphosphonium salt of the present invention is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1.7:2.
Simple production method: carry out according to the following step successively,
Its preparation method carries out according to the following step successively:
(1) glutaraldehyde and tetra methylol sulfuric acid phosphonium are added in reactor under normal temperature, stir 5-10 minute;
(2) again by the mixed liquor of tributyltetradecylphchloridem chloridem and isothiazolinone step (1), 10-15 minute is stirred;
(3) finally dithiocyano-methane and deionized water are added in the mixed liquor that step (2) obtains, stir 10-15 minute to obtain finished product.
Good effect of the present invention is adopted to be: on the basis of existing technology, pass through long term test, we find by adjusting the composition of quaternary alkylphosphonium salt and proportioning, in conjunction with adjustment product composition, by adding dithiocyano-methane, good coordinating effect is created between each component, the discovery that we are surprised, the compound disinfectant finally obtained all has very excellent bactericidal effect, and can use in the recirculated cooling water of high ph-values condition, to heterotroph, sulfate reducing bacteria, algae has excellent killing effect, especially obvious to heterotroph killing effect, speed of killing livestock is fast, power of killing livestock is strong, toxicity is little, good water solubility, easily biological-degradable, dosage is little, microorganism not easily develops immunity to drugs, not easy to foaming, synergistic effect is good.This high efficiency composition bactericide sterilization algae removal speed is fast, consumption is few, and non-foaming foam, material therefor easily biological-degradable, is beneficial to commercial Application.
Embodiment
Below in conjunction with the embodiment of the application, the technical scheme of the application is described in detail, but following embodiment is only understand the present invention, and the application can not be limited, embodiment in the application and the feature in embodiment can combine mutually, and the multitude of different ways that the application can be defined by the claims and cover is implemented.
Embodiment 1
High efficiency composition bactericide of the present invention, its ingredients by weight percentage composition is: glutaraldehyde 15%, quaternary alkylphosphonium salt 42%, isothiazolinone 11%, deionized water 24%, dithiocyano-methane 8%.Wherein quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1.7:2
Its preparation method carries out according to the following step successively:
(1) glutaraldehyde and tetra methylol sulfuric acid phosphonium are added in reactor under normal temperature, stir 5 minutes;
(2) again by the mixed liquor of tributyltetradecylphchloridem chloridem and isothiazolinone step (1), stir 10 minutes;
(3) finally dithiocyano-methane and deionized water are added in the mixed liquor that step (2) obtains, stir 10 minutes to obtain finished product.
By the following test, result of use of the present invention is described.
1) test method: the high efficiency composition bactericide adding doses in water sample, contact certain hour at 35 ± 2 DEG C after, according to the analytical method of industrial circulating cooling water defined, remaining heterotroph number is measured with plate count, make blank sample simultaneously, contrast with former water sample bacteria containing amount and obtain sterilizing rate.
Table 1 high efficiency composition bactericide is to the killing effect of heterotroph
2) according to the analytical method of industrial circulating cooling water defined, fungi bactericidal effect is measured with plate count
Table 2 high efficiency composition bactericide is to the killing effect of fungi
3) according to the analytical method of industrial circulating cooling water defined, sulfate reducing bacteria bactericidal effect is measured by MPN method
Table 3 high efficiency composition bactericide is to the killing effect of sulfate reducing bacteria
4) by spectrophotometry algal inhibition rate, test algae kind is common core chlorella
Table 4 high efficiency composition bactericide is to the killing effect of algae
Embodiment 2
High efficiency composition bactericide of the present invention, its ingredients by weight percentage composition is: glutaraldehyde 16%, quaternary alkylphosphonium salt 44%, isothiazolinone 15%, deionized water 20%, dithiocyano-methane 5%.Wherein quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1.7:2
Its preparation method carries out according to the following step successively:
(1) glutaraldehyde and tetra methylol sulfuric acid phosphonium are added in reactor under normal temperature, stir 10 minutes;
(2) again by the mixed liquor of tributyltetradecylphchloridem chloridem and isothiazolinone step (1), stir 15 minutes;
(3) finally dithiocyano-methane and deionized water are added in the mixed liquor that step (2) obtains, stir 15 minutes to obtain finished product.
By the following test, result of use of the present invention is described.
1) test method: the high efficiency composition bactericide adding doses in water sample, contact certain hour at 35 ± 2 DEG C after, according to the analytical method of industrial circulating cooling water defined, remaining heterotroph number is measured with plate count, make blank sample simultaneously, contrast with former water sample bacteria containing amount and obtain sterilizing rate.
Table 5 high efficiency composition bactericide is to the killing effect of heterotroph
2) according to the analytical method of industrial circulating cooling water defined, fungi bactericidal effect is measured with plate count
Table 6 high efficiency composition bactericide is to the killing effect of fungi
3) according to the analytical method of industrial circulating cooling water defined, sulfate reducing bacteria bactericidal effect is measured by MPN method
Table 7 high efficiency composition bactericide is to the killing effect of sulfate reducing bacteria
4) by spectrophotometry algal inhibition rate, test algae kind is common core chlorella
Table 8 high efficiency composition bactericide is to the killing effect of algae
Comparative example 1
Wherein quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1:2, and all the other are identical with embodiment 1.
Killing effect mainly for heterotroph is tested, and test condition is equal to embodiment 1 completely
Table 9 high efficiency composition bactericide is to the killing effect of heterotroph
Comparative example 2
Wherein quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1:1, and all the other are identical with embodiment 1.
Killing effect mainly for heterotroph is tested, and test condition is equal to embodiment 1 completely
Table 10 high efficiency composition bactericide is to the killing effect of heterotroph
Can find out that the adding proportion of tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem all has remarkable impact to the killing effect of heterotroph and Continuous sterilization time by comparative example 1 and 2, we find to work as proportionate relationship both it is that 1.7:2 is obviously better than other proportionate relationships.
Comparative example 3
Wherein deionized water 25%, does not add dithiocyano-methane, and all the other are identical with embodiment 2.
Killing effect mainly for heterotroph is tested, and test condition is equal to embodiment 2 completely
Table 11 high efficiency composition bactericide is to the killing effect of heterotroph
These are only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various change and conversion.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. a high efficiency composition material of germicide, is characterized in that it is composed of the following components: glutaraldehyde 15%-18%, quaternary alkylphosphonium salt 42%-49%, isothiazolinone 11%-17%, deionized water 20%-30%, dithiocyano-methane 5-8%; Said components is weight percentage.
2. compound disinfectant raw material according to claim 1, is characterized in that, described quaternary alkylphosphonium salt is tetra methylol sulfuric acid phosphonium and tributyltetradecylphchloridem chloridem, and the mass ratio of the two is 1.7:2.
3. prepare a method for claim 1-2 compound disinfectant raw material described in one of them, it is characterized in that, comprise the following steps:
(1) glutaraldehyde and tetra methylol sulfuric acid phosphonium are added in reactor under normal temperature, stir 5-10 minute;
(2) again by the mixed liquor of tributyltetradecylphchloridem chloridem and isothiazolinone step (1), 10-15 minute is stirred;
(3) finally dithiocyano-methane and deionized water are added in the mixed liquor that step (2) obtains, stir 10-15 minute to obtain finished product.
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| CN104488957B CN104488957B (en) | 2016-08-24 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105076201A (en) * | 2015-09-09 | 2015-11-25 | 郑州轻工业学院 | Complex oilfield water flooding bactericide |
| CN105104420A (en) * | 2015-08-04 | 2015-12-02 | 威海翔宇环保科技股份有限公司 | Fungicide for compound oilfield reinjection water, and preparation method therefor |
| CN107996600A (en) * | 2017-12-12 | 2018-05-08 | 长沙拜特生物科技研究所有限公司 | Improver of water quality and preparation method thereof |
| CN108308194A (en) * | 2018-04-20 | 2018-07-24 | 东莞市顶盛环保科技有限公司 | A kind of composite multifunction fungicide |
| CN108378058A (en) * | 2018-03-23 | 2018-08-10 | 山东天庆科技发展有限公司 | A kind of fungicide and preparation method thereof for Used in Seawater Circulating System |
| CN108849909A (en) * | 2018-09-13 | 2018-11-23 | 科得邦（江苏）环境科技有限公司 | A kind of cleaning air conditioner efficient sterilizing algicide |
| CN109221240A (en) * | 2018-11-01 | 2019-01-18 | 西安石油大学 | A kind of water system inhibits the high efficiency composition disinfecting corrosion inhibitor of simultaneously decomposing organism film |
| CN110326616A (en) * | 2019-04-16 | 2019-10-15 | 骏雁新材料科技（上海）有限公司 | A kind of cationic polymerization Biocidal algae-killing agent and its manufacturing method |
| CN111226951A (en) * | 2020-01-18 | 2020-06-05 | 浙江先拓环保科技有限公司 | Water treatment bactericide and preparation method thereof |
| CN112704077A (en) * | 2020-12-29 | 2021-04-27 | 新疆水处理工程技术研究中心有限公司 | Non-oxidation bactericide and preparation method thereof |
| CN113796389A (en) * | 2021-09-06 | 2021-12-17 | 鞍钢栗田(鞍山)水处理有限公司 | Composite bactericide suitable for blast furnace closed circulating water and preparation and use methods thereof |
| CN113875777A (en) * | 2021-11-17 | 2022-01-04 | 山东天庆科技发展有限公司 | Non-oxidative sterilization algicide for circulating water and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105104420A (en) * | 2015-08-04 | 2015-12-02 | 威海翔宇环保科技股份有限公司 | Fungicide for compound oilfield reinjection water, and preparation method therefor |
| CN105076201A (en) * | 2015-09-09 | 2015-11-25 | 郑州轻工业学院 | Complex oilfield water flooding bactericide |
| CN107996600A (en) * | 2017-12-12 | 2018-05-08 | 长沙拜特生物科技研究所有限公司 | Improver of water quality and preparation method thereof |
| CN108378058A (en) * | 2018-03-23 | 2018-08-10 | 山东天庆科技发展有限公司 | A kind of fungicide and preparation method thereof for Used in Seawater Circulating System |
| CN108308194A (en) * | 2018-04-20 | 2018-07-24 | 东莞市顶盛环保科技有限公司 | A kind of composite multifunction fungicide |
| CN108849909A (en) * | 2018-09-13 | 2018-11-23 | 科得邦（江苏）环境科技有限公司 | A kind of cleaning air conditioner efficient sterilizing algicide |
| CN109221240A (en) * | 2018-11-01 | 2019-01-18 | 西安石油大学 | A kind of water system inhibits the high efficiency composition disinfecting corrosion inhibitor of simultaneously decomposing organism film |
| CN110326616A (en) * | 2019-04-16 | 2019-10-15 | 骏雁新材料科技（上海）有限公司 | A kind of cationic polymerization Biocidal algae-killing agent and its manufacturing method |
| CN111226951A (en) * | 2020-01-18 | 2020-06-05 | 浙江先拓环保科技有限公司 | Water treatment bactericide and preparation method thereof |
| CN112704077A (en) * | 2020-12-29 | 2021-04-27 | 新疆水处理工程技术研究中心有限公司 | Non-oxidation bactericide and preparation method thereof |
| CN113796389A (en) * | 2021-09-06 | 2021-12-17 | 鞍钢栗田(鞍山)水处理有限公司 | Composite bactericide suitable for blast furnace closed circulating water and preparation and use methods thereof |
| CN113875777A (en) * | 2021-11-17 | 2022-01-04 | 山东天庆科技发展有限公司 | Non-oxidative sterilization algicide for circulating water and preparation method thereof |
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