CN101731269A - Silver/manganese composition with high valent state and application thereof - Google Patents

Silver/manganese composition with high valent state and application thereof Download PDF

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Publication number
CN101731269A
CN101731269A CN200810202418A CN200810202418A CN101731269A CN 101731269 A CN101731269 A CN 101731269A CN 200810202418 A CN200810202418 A CN 200810202418A CN 200810202418 A CN200810202418 A CN 200810202418A CN 101731269 A CN101731269 A CN 101731269A
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legionella
silver
water
composition
bactericide
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CN101731269B (en
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陈康
周国光
焦莉莉
冯长春
高庆华
张琴
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SHANGHAI DUOJIA WATER PROCESSING SCI-TECH Co Ltd
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SHANGHAI DUOJIA WATER PROCESSING SCI-TECH Co Ltd
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Abstract

The invention relates to a silver (III)/manganese composition with high valent state and an application thereof. The composition comprises a water solution of a halogen coordination compound of trivalent silver and a water solution of water soluble permanganate; measured by Ag, the mass ratio of the halogen coordination compound of the trivalent silver to the water soluble permanganate is 1:(1-10); and measured by the Ag in a similar way, the concentration of the trivalent silver is 1000-10000mg/L, and the halogen is Cl, Br or I. The silver (III)/manganese composition with high valent state can be used as a bactericide, carries out sterilization and disinfection treatment on the bacteria (which are microorganisms comprising legionnella and heterotrophic bacteria) of the circulating cooling water of an air conditioner and is a green bactericide which has favorable stability (thermal stability and chemical stability), unique sterilization broad spectrum and safety to people and equipment and is friendly to the environment.

Description

Silver/manganese composition with high valent state and uses thereof
Technical field
The present invention relates to a kind of high valence state silver (III)/manganese composition and uses thereof.
Background technology
Legionella (legionella) is a kind of water source microorganism, but does not form gemma, no pod membrane, thermophilicly is afraid of cold, at water temperature long-term surviving under 31 ℃~36 ℃ natural conditions, belongs to aerobic gram-Negative bacillus.Having a liking for lung Legionella (legionellapneumophila) is modal pathogenic bacteria in the Legionnella, and about l more than 90% is to be caused by it.
One of lung Legionella (legionella pneumophila) main parasitic ground, their existence, the health that will endanger people are had a liking for by the cooling circulation cooling water of air conditioner system.Therefore, kill how quickly, simple and efficient and have a liking for extremely people's attention of lung Legionella (legionella pneumophila) in the cooling circulation cooling water of air conditioner system.
So far, killing the most frequently used method of Legionella in the cooling circulation cooling water of air conditioner system (legionella) is to adopt chemical bactericide to sterilize.The chemical bactericide that has been used comprises: chloride series bactericidal agent, metal ion series bactericidal agent and aldehydes bactericide, but effect is all undesirable.As main glutaraldehyde and 20%-30% quaternary ammonium salt composite bactericide by 20%-30% that CN 1853468A is reported, when adding concentration 50mg/L, contact in the time of 4 hours, sterilizing rate can reach more than 99%.But glutaraldehyde is oxidized to glutaric acid easily, thereby causes equipment and pipeline corrosion.
U.S.'s heat supply in 2000, refrigeration and air-conditioning association (ASHRAE) are in " reducing the harm of building water system Legionella " policy paper, copper silver (I) ion method is recommended as a kind of main method of controlling Legionella in the building water system, copper silver ion concentration is controlled to be 0.4mg/L and 0.04mg/L respectively.But high copper ion like this is obviously inappropriate in recirculated cooling water, causes the serious galvanic corrosion of steel or aluminium alloy because copper ion can form the light current pond with hardware carbon steel or aluminum alloy surface, the service life of reducing equipment.The silver of lower valency is easy to the chlorion generation silver nitride precipitation in the water in addition, reduces bactericidal effect.
For this reason, seek a kind of new method of killing Legionella in the cooling circulation cooling water of air conditioner system (legionella), in other words, a kind of bactericide of can highly effective and safe killing Legionella (legionella) of development just becomes the technical problem that this area presses for solution (to people and equipment).
Summary of the invention
The present inventor is through extensive and deep discovering: the cooling circulation cooling water of air conditioner system why become easily Legionella (legionella)-particularly have a liking for lung Legionella (legionella pneumophila)-grow and the breeding spot, remove because the water environment of cooling circulation cooling water of air conditioner system is that growing of Legionella (legionella) and breeding provide optimum life condition (suitable water temperature, sunlight and abundant nutrition) outside, also because there are a large amount of microbiologic populations that are fit to Legionella (legionella) growth in the cooling circulation cooling water of air conditioner water body, these micropopulations drop on pipeline or the water tank inner surface forms biomembrane, for protozoic growth provides the place.This biomembrane seriously influences diffusion of sterilant simultaneously, and bactericidal effect is obviously reduced.Be grown in biomembrane inside or colonize in the interior Legionella of protozoa body, can escape the influence of extraneous adverse circumstances greatly, and existing bactericide in the biomembrane or the Legionella in the protozoa body (legionella) be difficult to play a role, have a strong impact on sterilization effect.
Given this, the present inventor provides a kind of high valence state silver (III)/manganese composition, show through bactericidal assay: it can not only kill the Legionella (legionella) of " swimming ", and can kill colonize in the biomembrane or the protozoa body in the Legionella (legionella) of killing particularly have a liking for lung Legionella (Iegionella pneumophila) and other bacterium, and to the equal safety of people and equipment.
The said silver/manganese composition with high valent state of the present invention, it is made up of the aqueous solution of the halogen complex of trivalent silver and the aqueous solution of water-soluble permanganate;
Wherein: in Ag, the halogen complex of trivalent silver and the mass ratio of water-soluble permanganate are 1: (1~10), and, equally in Ag, the concentration of trivalent silver is 1,000mg/L~10,000mg/L (L represents one liter of described composition); Said halogen is Cl, Br or I.
High valence state silver of the present invention (III)/manganese composition can be used as: kill Legionella (legionella)-particularly and colonize in the bactericide of having a liking for lung Legionella (legionella pneumophila) in the cooling circulation cooling water of air conditioner.
Description of drawings
It is the back effect schematic diagram (the sterilization processing time is 2.5 hours) that bactericide is killed Legionella (legionella) that Fig. 1 adopts composition of the present invention at certain central air-conditioning recirculating cooling water system;
It is the back effect schematic diagram (the sterilization processing time is 2.5 hours) that bactericide is killed heterotroph (heterotrophic bacteria) that Fig. 2 adopts composition of the present invention at certain central air-conditioning recirculating cooling water system;
It is effect schematic diagram after bactericide carries out sterilization processing (the sterilization processing time is 7 days) that Fig. 3 adopts composition of the present invention at certain central air-conditioning recirculating cooling water system;
Wherein: Fig. 3-a is for killing the effect schematic diagram of Legionella (legionella); Fig. 3-b is for killing the effect schematic diagram of heterotroph (heterotrophicbacteria).
Embodiment
A kind of method of preparation high valence state silver of the present invention (III)/manganese composition, it comprises the steps:
(1) preparation of the halogen complex of high price silver (III):
Water-soluble monovalence silver salt [brief note is: water-soluble silver (I) salt] is dissolved in the water silver-coloredly (I) saline solution, add ligand compound, activator, stabilizing agent and water again, (speed of agitator is to be controlled at 200 rev/mins~1 in stirring, be advisable for 000 rev/min) and be heated to 50 ℃~95 ℃, and keep getting in 2 hours~8 hours the halogen complex of high price silver (III) at this state;
Wherein: the mol ratio of water-soluble silver (I) salt, ligand compound, activator and stabilizing agent is 1: (2~10): (2~10): (10~30); Said ligand compound is potassium hyperchlorate, sodium perchlorate, hyperbromic acid potassium, hyperbromic acid sodium, potassium metaperiodate or sodium metaperiodate; Said activator potassium peroxydisulfate or sodium peroxydisulfate; Said stabilizing agent is a caustic alkali.
(2) preparation of object (high valence state silver (III)/manganese composition):
With the water-soluble aqueous solution that gets permanganate of water-soluble permanganate (as potassium permanganate or sodium), the aqueous solution of heating gained permanganate is to boiling, stop heating, the cooling back moves in the brown bottle left standstill 168 hours at least, filter, gained filtrate by aforementioned ratio with promptly get object after high price silver (III) the halogen complex that is made by step (1) mixes.
The evaluation of high valence state silver of the present invention (III)/manganese composition bactericidal property:
1, to the bactericidal property evaluation of Legionella (legionella):
According to Ministry of Health of the People's Republic of China's promulgation in 2003 " public place centralized air ventilation system hygienic practice " appendix A, entrust Shanghai City preventive medicine research institute that high valence state silver of the present invention (III)/manganese composition is carried out the evaluation of Legionella (legionella) bactericidal property:
1) material instrument
A. bactericide: high valence state silver of the present invention (III)/manganese composition;
B. test strain: legionella pneumophilia 1 type (ATCC 33152), concentration 6.35 * 10 6
C. Legionella dilution: sterile distilled water, bactericide dilution: sterilization hard water;
D. medium: GVPC flat board (French Biomerieux SA);
E. instrument: contain 2.5%CO 237 ℃ of incubators, Biohazard Safety Equipment.
2) measurement result sees Table 1
The high valence state silver of table 1 (III)/manganese composition is to the bacteriostasis rate of legionella pneumophilia (legionella pneumophila)
Figure G2008102024185D0000031
Annotate: the negative control asepsis growth
2. to the bactericidal property evaluation of heterotroph (heterotrophic bacteria):
Heterotroph (heterotrophic bacteria) is meant and utilizes the class mixed bacterial of organic carbon compound as carbon nutrition and energy source.Heterotroph (heterotrophic bacteria) not only breed fast and also quantity many, can represent the bacterial population in the water body to a great extent, so generally when microorganisms in water detects, normal quantity with this bacterioid is as total number of bacteria.State Standard of the People's Republic of China's " Code for design of industrial recirculating cooling water treatment " clearly stipulates that heterotroph in the circulation (heterotrophic bacteria) number is less than 1 * 10 in (GB50050-2007) 5Individual/ml.Heterotroph (heterotrophic bacteria) and Legionella (legionella) coexistence one in addition helps suppressing growing of Legionella (legionella) and kills killing of heterotroph (heterotrophic bacteria).Therefore, select heterotroph (heterotrophic bacteria) when bactericidal property is estimated, have bigger representativeness and practical significance as sterilization object.
1) experimental technique: the mensuration-test bottle method of heterotroph (heterotrophic bacteria) number:
The disappearance dilution method is adopted in the test bottle method test of heterotroph (heterotrophic bacteria) number, promptly the water sample of needs test being injected test bottle step by step dilutes, to the last in test bottle till the aseptic appearance, according to extension rate, calculate the quantity of heterotroph in the water sample then.
2) measurement result sees Table 2
The high valence state silver of table 2 (III)/manganese composition is to the sterilizing rate of heterotroph (heterotrophic bacteria)
Figure G2008102024185D0000041
By last table 1, table 2 as can be known, high valence state silver of the present invention (III)/manganese composition has extremely strong susceptibility and wholesomeness (the Legionella sterilizing rate reaches 99.99%) to Legionella (legionella), and sterilization is quick; Simultaneously heterotroph (heterotrophicbacteria) is also had and well kill and inhibitory action.
With high valence state silver of the present invention (III)/manganese composition is bactericide, cooling circulation cooling water of air conditioner is being carried out sterilization (microorganism that comprises Legionella (legionella) and heterotroph (heterotrophic bacteria)) when disinfecting, in Ag, the suitable concentration of bactericide is 0.01mg/L 1~10mg/L 1(L 1Be one liter of water yield for the treatment of that sterilizing is handled, down together), concrete processing method comprises the steps:
Said disinfecting comprises the steps:
I) when Legionella clump count in the pending cooling circulation cooling water of air conditioner 〉=1000cfu/ml:
At first acrylate-co-polymer of sulfonate (dispersant) is added in the pending cooling circulation cooling water of air conditioner, make that dispersant concentration is 10mg/L in the recirculated cooling water 1~50mg/L 1Add high valence state silver of the present invention (III)/manganese composition in the impact type mode then, in Ag, making described high valence state silver (the III)/concentration of manganese composition in recirculated cooling water is 1mg/L 1~10mg/L 1Continuously running 1 hour~24 hours (during staying water do not discharge, in order to avoid contaminated environment and reduction concentration of sterilant) after, system is killed biomembranous thorough cleaning, removes mud and dirt layer, pre-then film, transfer normal operation again to, in Ag, the concentration that makes high valence state silver of the present invention (III)/manganese composition in the cooling circulation cooling water of air conditioner is 0.01mg/L 1~0.5mg/L 1
Ii) when in the pending cooling circulation cooling water of air conditioner: during 10cfu/ml≤Legionella clump count<1000cfu/ml:
At first successively acrylate-co-polymer of sulfonate (dispersant) and high valence state silver of the present invention (III)/manganese composition (bactericide) is added in the pending cooling circulation cooling water of air conditioner, make that dispersant concentration is 10mg/L in the recirculated cooling water 1~50mg/L 1, add high valence state silver of the present invention (III)/manganese composition then, in Ag, making the concentration of bactericide in recirculated cooling water is 0.5mg/L 1~5mg/L 1, turn round continuously 1 hour~24 hours (during recirculating cooling water system can not stop normal operation), as long as make the concentration (in Ag) of bactericide in the cooling circulation cooling water of air conditioner maintain 0.01mg/L then 1~0.5mg/L 1Get final product.
Iii) when Legionella clump count in the pending cooling circulation cooling water of air conditioner<10cfu/ml
As long as make the concentration of bactericide in the pending cooling circulation cooling water of air conditioner,, maintain 0.01mg/L in Ag 1~0.5mg/L 1Can meet the requirement of " public place centralized air ventilation system hygienic practice ", system can normally move.
In summary, high valence state silver of the present invention (III)/manganese composition is a kind of sterilization wide spectrum, safety (to people and equipment) and environment amenable " green " bactericide with good stability (heat endurance and chemical stability), uniqueness.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention:
Embodiment 1
The preparation of high valence state silver manganese compound disinfectant may further comprise the steps:
1) preparation of the silver-colored halogen complex of bactericidal activity component high price
A. get silver nitrate 78.8g, join in the 1000ml water, stirring and dissolving becomes silver nitrate aqueous solution.
B. add 3000ml water in stirred tank, add potassium hydroxide 663g then, open and stir, 300 rev/mins of rotating speeds add activator potassium hyperchlorate 320g again, continue to stir, and are heated to 60 ℃ simultaneously, add activator potassium peroxydisulfate 300g again, are stirred to dissolving.
When treating that c. temperature rises to 60 ℃, a, b are mixed, continue to stir 3 hours.
D. stop to stir, be cooled to room temperature, promptly get the silver-colored halogen complex aqueous solution of bactericidal activity component high price.
2) preparation of bactericidal activity component stability permanganate water solution
A. get potassium permanganate 50g and add in the 2000ml water, heated and stirred is dissolved to little boiling, and is cooled to room temperature then, and deposits in the brown bottle.
B. with above-mentioned one week of solution left standstill, filter, get filtrate, obtain stable permanganate water solution with the glass sand core funnel, standby.
3) preparation of high valence state silver manganese compound disinfectant
The aforementioned stable permanganate water solution is added in the silver-colored halogen complex aqueous solution of high price, and adding entry to cumulative volume simultaneously is 10L, stirs, and promptly getting the high price silver content is 5000mg/L (in Ag) object.
Embodiment 2
Bactericide of the present invention is applied to certain central air-conditioning recirculating cooling water system, and it is 1 * 10 that this system initially records the heterotroph number 6Individual/ml, Legionella clump count is 800cfu/ml.Take to add the mode of bactericide, and regularly water sampling is measured wherein heterotroph (heterotrophic bacteria) and Legionella (legionella) number (Legionella detects unit-Shanghai City preventive medicine research institute by Shanghai City Legionella fixed point and detects) in cooling tower tower tray place one-shot formula.In Ag, the concentration of bactericide in recirculated cooling water is 2mg/L 1, a sterilization processing 2.5 hours and a week, its result is referring to Fig. 1, Fig. 2 and Fig. 3.
By Fig. 1 and Fig. 2 as can be known: sterilization operation 10 minutes, heterotroph in the system (heterotrophic bacteria) number is reduced to and is not detected, Legionella (legionella) clump count is also reduced to and is not detected, all keep not detecting until 2.5h heterotroph (heterotrophic bacteria) and Legionella (legionella), illustrate that bactericide impact type bactericidal effect of the present invention is good.
As shown in Figure 3: all circulation control of microorganisms are good, and Legionella (legionella) clump count keeps not detecting, and heterotroph (heterotrophic bacteria) clump count is 1 * 10 3In individual/ml, be significantly less than national standard 1 * 10 5Individual/ml, illustrate that bactericide of the present invention has good sterilization continuation.
Recirculating cooling water system makes circulation high price silver content maintain 0.05mg/L after having carried out the impact type sterilization in the above-mentioned application 1~0.1mg/L 1In the scope, repeatedly to this systemic circulation water sampling, testing result shows that system water sample Legionella (legionella) does not detect through Shanghai City preventive medicine research institute, and heterotroph (heterotrophic bacteria) number is 1 * 10 3In individual/ml, illustrate that high valence state silver manganese compound disinfectant all has the Legionella in the cycle water and heterotroph well to kill and control action.

Claims (7)

1. a silver/manganese composition with high valent state is characterized in that, said composition is made up of the aqueous solution of the halogen complex of trivalent silver and the aqueous solution of water-soluble permanganate;
Wherein: in Ag, the halogen complex of trivalent silver and the mass ratio of water-soluble permanganate are 1: (1~10), and equally in Ag, the concentration of trivalent silver is 1,000mg/L~10, and 000mg/L, said halogen are Cl, Br or I.
2. composition as claimed in claim 1, it is characterized in that, the halogen complex of wherein said trivalent silver by: monovalence water soluble silver salt be dissolved in the water the aqueous solution of monovalence water soluble silver salt, mix with ligand compound, activator, stabilizing agent and water again, stirring also is heated to 50 ℃~95 ℃, and keeps making in 2 hours~8 hours at this state;
Wherein: the mol ratio of monovalence water soluble silver salt, ligand compound, activator and stabilizing agent is 1: (2~10): (2~10): (10~30).
3. composition as claimed in claim 2 is characterized in that, wherein said ligand compound is potassium hyperchlorate, sodium perchlorate, hyperbromic acid potassium, hyperbromic acid sodium, potassium metaperiodate or sodium metaperiodate.
4. composition as claimed in claim 2 is characterized in that, wherein said activator potassium peroxydisulfate or sodium peroxydisulfate; Said stabilizing agent is a caustic alkali.
5. kill the bactericide of Legionella (legionella) and heterotroph (heterotrophic bacteria) as any described composition conduct in the claim 1~4.
6. purposes as claimed in claim 5 is characterized in that, wherein said Legionella (legionella) is legionella pneumophilia (legionella pneumophila).
7. as any application of described composition in the sterilization treatment of cooling circulation cooling water of air conditioner in the claim 1~4.
CN2008102024185A 2008-11-07 2008-11-07 Silver/manganese composition with high valent state and application thereof Expired - Fee Related CN101731269B (en)

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