CN111869679B - Bactericide and preparation method and application thereof - Google Patents
Bactericide and preparation method and application thereof Download PDFInfo
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- CN111869679B CN111869679B CN202010743340.9A CN202010743340A CN111869679B CN 111869679 B CN111869679 B CN 111869679B CN 202010743340 A CN202010743340 A CN 202010743340A CN 111869679 B CN111869679 B CN 111869679B
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- bactericide
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 99
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 51
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 62
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 59
- 239000002131 composite material Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 43
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 29
- 235000010413 sodium alginate Nutrition 0.000 claims description 29
- 239000000661 sodium alginate Substances 0.000 claims description 29
- 229940005550 sodium alginate Drugs 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 30
- 230000001954 sterilising effect Effects 0.000 abstract description 25
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- -1 iron ions Chemical class 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 10
- 101710134784 Agnoprotein Proteins 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 244000005700 microbiome Species 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 206010059866 Drug resistance Diseases 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a bactericide, a preparation method and application thereof, wherein the bactericide comprises a carrier, and AgO and FeOOH loaded on the carrier, and the carrier contains TiO 2 AgO can slowly release Ag in water 2+ The FeOOH has strong sterilization performance, can utilize iron ions dissolved in circulating water to form iron circulation, accelerates the transmission of carriers and promotes AgO and TiO 2 The components in the bactericide are mutually cooperated, so that the bactericide has the effects of sterilization and photocatalysis purification. Meanwhile, the preparation method of the bactericide and the application of the bactericide in circulating water are provided.
Description
Technical Field
The invention relates to the technical field of bactericides, in particular to a bactericide for circulating water and a preparation method and application thereof.
Background
The problem of water resources is increasing, and the treatment and recycling of industrial water are necessary to realize the sustainable development of economy, with the Chinese fresh water accounting for only 7% of the world. And pollution of the industrial circulating water system is mainly caused by microorganisms in the industrial circulating water system. On the one hand, microorganisms cause direct pollution of the water body; on the other hand, microorganisms in industrial circulating water bring great harm to equipment, a large amount of slime is generated by the microorganisms, corrosion is caused in the circulating water, the slime covers metal to generate oxygen concentration to corrode a battery, iron is dissolved, scale formation is generated by accumulation of the slime to prevent heat conduction, and pipelines are seriously blocked. Therefore, the control and reduction of the microorganism content in the circulating water are key to maintaining the water quality and prolonging the service life of the instrument.
In the current circulating water treatment technology, bactericides are often adopted to control the propagation of microorganisms. The bactericide interferes with and destroys a certain aspect of the microbial life activities, thereby achieving the effect of controlling the microbial reproduction, protecting equipment, prolonging the service life of the equipment, saving water and energy.
The common circulating water bactericides include chlorine dioxide, peroxide, bromine-based biocides, quaternary ammonium salts, glutaraldehyde and the like. However, these fungicides have their own limitations. If the use of chlorine dioxide brings serious chlorine pollution to water and environment, the sterilization technology gradually approaches to non-chlorine materials; the temperature, acid-base property and metal ion impurities of the circulating water bring a certain limit to the use of peroxide; the organic bactericides such as quaternary ammonium salts have the problem of drug resistance, and the bactericides need to be replaced frequently.
The conventional circulating water sterilization technology has serious pollution to water bodies and generally has the problem of drug resistance, and a single bactericide has large dosage and unobvious sterilization performance, so that a plurality of bactericides are required to be compounded for use, and the bactericide has obvious synergistic effect. Currently, the bactericide is developed from a single function type to a multifunctional composite type, so that the development of the efficient broad-spectrum composite bactericide is of great significance.
Disclosure of Invention
The invention aims to solve the problems of secondary environmental pollution, high limitation of use environment, microbial resistance and the like of the conventional circulating water bactericide, and has low microbial killing rate on water body, and the bactericide needs to be frequently supplemented in the actual use process. These problems lead to a series of problems of poor quality of circulating water, poor cooling effect, large dosage of bactericide and the like in actual production. Therefore, the bactericide provided by the invention has the effects of sterilization and photocatalysis purification, can be applied to an open cooling tower, has high-efficiency and broad-spectrum sterilization effect on circulating water, and can effectively inhibit and kill microorganisms in the circulating water.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a bactericide comprising: the carrier and AgO and FeOOH loaded on the carrier.
AgO can slowly release Ag 2+ High-valence Ag 2+ Has strong bactericidal performance, and the bactericidal effect is low-price Ag + About 200 times of the total amount of the water, the AgO has a certain photocatalysis effect, electrons and holes are generated after the AgO is excited by light, and FeOOH (iron oxyhydroxide) exists, so that the photocatalysis process of the AgO can be promoted, and the sterilization performance is improved, because a large amount of impurity iron ions exist in circulating water, the FeOOH and the impurity iron form iron circulation, and the iron circulation can accelerate the transmission of carriers (electrons and holes), so that the photocatalysis process is promoted.
Further, the mass of AgO is 5-15% of the mass of the carrier, and the mass of FeOOH is 1-10% of the mass of the carrier. If the amount of AgO or FeOOH is too large, the number of carriers is too large, which may cause carrier recombination, and the photocatalytic effect is reduced or lost.
In particular embodiments of the invention, the AgO mass is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., of the vector mass.
In particular embodiments of the invention, the FeOOH mass is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., of the vector mass.
Further, the carrier comprises TiO 2 。
TiO 2 Has photocatalysis effect, is excited by light, generates electrons and holes, and has photocatalysis sterilization effect. With Ag 2+ Compared with the rapid and high-efficiency sterilization effect of TiO 2 Is sterilized by photocatalysisThe process is relatively slow, but the sterilization effect is durable, so that AgO and TiO 2 The two components form complementary functions, so that the bactericide product has lasting and efficient bactericidal effect.
Further, the carrier is TiO 2 Supports or TiO 2 /Al 2 O 3 And (3) a composite carrier.
In a specific embodiment of the invention, the germicides are: tiO (titanium dioxide) 2 The carrier and AgO and FeOOH loaded on the carrier.
In a specific embodiment of the invention, the germicides are: tiO (titanium dioxide) 2 /Al 2 O 3 Composite carrier and AgO, feOOH loaded on the composite carrier.
Al 2 O 3 The porous structure can play a role in dispersing and stabilizing effective sterilization components, can adsorb impurities in circulating water, and promotes a photocatalysis process.
Further, the TiO 2 /Al 2 O 3 In the composite carrier, tiO 2 The mass is Al 2 O 3 10 to 30 percent of the mass. Within this range, tiO 2 Can be well loaded on Al 2 O 3 And fully plays the photocatalytic sterilization role.
In a specific embodiment of the present invention, the TiO 2 The mass is Al 2 O 3 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30% by mass, etc.
Further, the TiO 2 Supports or TiO 2 /Al 2 O 3 The particle size of the composite carrier is 30 to 150. Mu.m, preferably 30 to 75. Mu.m.
Further, the TiO 2 /Al 2 O 3 The preparation method of the composite carrier comprises the following steps:
(1) Mixing an aluminum source with water, stirring, adding a titanium source, adding acid liquor, and reacting at 80-100 ℃ for 7-9 hours to obtain a mixed solution;
(2) Spray drying the mixed solution in ammonia atmosphere to obtain TiO 2 /Al 2 O 3 A composite powder;
(3) The TiO is prepared 2 /Al 2 O 3 Soaking the composite powder in sodium hydroxide solution, washing, drying and roasting to obtain the TiO 2 /Al 2 O 3 And (3) a composite carrier.
Further, the aluminum source is provided by pseudo-boehmite powder. The main component of pseudo-boehmite is aluminum hydroxide, and aluminum oxide powder is generated in the high-temperature roasting stage.
Further, in the step (1), stirring is performed at 80-100 ℃ for 5-15 min.
Further, the titanium source is at least one of titanium sulfate, titanium nitrate and titanium chloride.
Further, the acid liquid is dilute nitric acid, preferably dilute nitric acid with a mass concentration of 8%.
Further, the concentration of the sodium hydroxide solution is 1 to 20%, preferably 5 to 10%.
In specific embodiments of the invention, the concentration of the sodium hydroxide solution is 5%, 6%, 7%, 8%, 9%, 10%, etc.
The purpose of soaking in sodium hydroxide solution is to react with the residual acid inside the carrier and deeply solidify TiO 2 /Al 2 O 3 And (3) a composite carrier. The soaking time is preferably 20-40 min.
Further, in the step (3), the drying temperature is 50-70 ℃, and the roasting is carried out for 4-6 hours at 500-700 ℃.
The prior art commonly uses an oil ammonia method to prepare TiO 2 /Al 2 O 3 Composite carrier, the particle size of the carrier is about 1-2mm, the TiO provided by the invention 2 /Al 2 O 3 In the preparation method of the composite carrier, spray drying is adopted in ammonia atmosphere, and compared with an oil-ammonia method, the preparation method has the advantages of simple operation, reduced ammonia water consumption, small and uniform carrier particle size and the like, and the TiO can be deeply solidified in the subsequent sodium hydroxide soaking operation 2 /Al 2 O 3 And (3) a composite carrier.
Further, the bactericide also contains sodium alginate, wherein the mass of the sodium alginate is 1-13% of that of AgO, and preferably 1-7%.
In particular embodiments of the invention, the mass of sodium alginate is 1%, 1.37%, 2%, 3%, 4%, 5%, 6%, 6.84%, 6.86%, 7%, 8%, 9%, 10%, 11%, 12%, 13% of the mass of AgO, and so on.
Further, the particle size of the bactericide is nano-scale, the specific particle size is below 50nm, and the nano-scale bactericide has higher efficient sterilization effect in the sterilization process.
In the bactericide provided by the invention, all the components are mutually cooperated, and the bactericide has the effects of sterilization and photocatalysis purification. Iron circulation of FeOOH accelerates carrier transmission and promotes AgO and TiO 2 Is combined with TiO by rapid sterilization of AgO 2 The slow sterilization of the utility model ensures that the bactericide has long-acting and lasting sterilization effect.
The bactericide provided by the invention is an inorganic bactericide, and has the advantages of broad spectrum, high efficiency, no drug resistance and the like compared with an organic bactericide.
In a second aspect, the present invention provides a method for preparing the above-mentioned bactericide, comprising the steps of:
s1, adding a carrier into an aqueous solution containing a ferric iron source and a monovalent silver source, and stirring to obtain a bactericide precursor solution;
s2, adding alkali liquor into the bactericide precursor solution, stirring, introducing oxidizing gas, filtering, and drying to obtain the bactericide.
Further, the ferric iron source is ferric nitrate; the monovalent silver source is at least one of silver nitrate and silver ammonia complex.
Further, in the step S1, before adding the carrier into the aqueous solution containing the ferric iron source and the monovalent silver source, sodium alginate is added into the aqueous solution, and the mixture is stirred for 20 to 40 minutes at room temperature.
Further, the addition amount of sodium alginate is 1 to 10% by mass, preferably 1 to 5% by mass of monovalent silver source.
In particular embodiments of the invention, sodium alginate is added in an amount of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., of the monovalent silver source mass.
The existence of the sodium alginate can not only disperse the generated AgO and FeOOH, but also react with calcium ions in the circulating water to generate calcium alginate, thereby achieving the purposes of absorbing the calcium ions and reducing the hardness of the water body.
Further, in the step S1, stirring is performed for 1 to 1.5 hours at room temperature.
Further, in the step S2, the alkali solution is at least one of sodium hydroxide and ammonia water.
Further, in the step S2, alkali liquor is added in a dropwise manner, and then stirred at room temperature for 5-15 min, wherein the dosage of the alkali liquor is that the ferric iron source and the monovalent silver source fully react.
Further, in the step S2, the concentration of the alkali solution is 1 to 20%, preferably 1 to 10%.
In a specific embodiment of the invention, in said step S2, the concentration of lye is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
Further, the oxidizing gas is a gas containing O 3 Or O 2 Can be pure O 3 Or pure O 2 Or a mixture of the two, or an inert gas and O 3 Or O 2 Is a mixed gas of (a) and (b).
In a specific embodiment of the invention, the oxidizing gas is: o (O) 3 、O 2 、O 3 /O 2 Mixed gas, O 3 /N 2 Mixed gas, O 2 /N 2 Mixed gas, and the like. By introducing oxidizing gas, ferric hydroxide is oxidized into FeOOH, ag + Oxidized to Ag 2+ 。
Further, in the step S2, the time for introducing the oxidizing gas is 20 to 40 minutes. During this time, the iron source and the silver source are fully oxidized.
In specific embodiments of the present invention, the oxidizing gas is introduced for a period of time of 20 minutes, 22 minutes, 24 minutes, 26 minutes, 28 minutes, 30 minutes, 32 minutes, 34 minutes, 36 minutes, 38 minutes, 40 minutes, and so on.
Further, in the step S2, the filtering and drying is specifically: filtering, washing and vacuum drying at 50-70 deg.c for 4-6 hr.
By the above preparation method, a bactericide having a particle diameter of at most 50nm, specifically, a bactericide having a particle diameter of at most nanometer can be obtained.
In a third aspect, the present invention provides the use of the above-described fungicide in circulating water.
The circulating water contains a large amount of iron ions and calcium ions, the iron ions and FeOOH in the bactericide form solid-phase to liquid-phase iron circulation, the carrier transmission is accelerated, the photocatalysis sterilization process is promoted, and sodium alginate in the bactericide can adsorb the calcium ions, so that the water hardness is reduced.
The invention has the beneficial effects that:
(1) In the bactericide provided by the invention, agO can slowly release Ag in water 2+ The sterilizing performance is strong, and heterotrophic bacteria in the circulating water can be effectively inhibited and killed;
(2) FeOOH can utilize dissolved iron ions in circulating water to form iron circulation so as to promote AgO and TiO 2 Is a photocatalytic process of (1);
(3) The sodium alginate added in the bactericide of the invention not only plays a role in dispersing AgO and FeOOH, but also can absorb Ca in circulating water 2+ The hardness of the circulating water is reduced;
(4)TiO 2 /Al 2 O 3 the carrier used as the bactericide can adsorb impurities in circulating water, and is prepared by spray drying under ammonia atmosphere, and has the characteristics of small particle size and uniform distribution;
(5) Compared with the organic bactericide, the inorganic bactericide provided by the invention has the advantages of spectrum, high efficiency, no drug resistance and the like.
Definition of terms
All ranges cited herein are inclusive unless clearly indicated to the contrary.
The terms "a" or "an" are used herein to describe the elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. Such description should be understood to include one or at least one, and the singular also includes the plural unless it is obvious that it is meant otherwise. "plurality of" means two or more.
The numbers in the present invention are approximations, by use of the antecedent "about" or "about" herein. The numerical values of the numbers may differ by 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number is disclosed having a value of N, any number having a value of N+/-1%, N+/-2%, N+/-3%, N+/-5%, N+/-7%, N+/-8% or N+/-10% will be explicitly disclosed, where "+/-" means plus or minus, and a range between N-10% and N+10% is also disclosed.
The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the 75 th edition handbook of chemistry and Physics, 1994. In addition, general principles of organic chemistry may be referenced to the descriptions in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato:1999, and "March's Advanced Organic Chemistry" by Michael b.smith and Jerry March, john Wiley & Sons, new york:2007, the entire contents of which are incorporated herein by reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless a particular paragraph is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Detailed Description
The following description is of the preferred embodiment of the present invention and is not intended to limit the invention, but is intended to cover any modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
The inventors have found that 40g of alumina powder can be obtained per 80g of pseudo-boehmite powder.
In the following examples, tiO 2 /Al 2 O 3 Composite support (20%) represents TiO 2 Occupying Al 2 O 3 20% by mass, likewise, tiO 2 /Al 2 O 3 Composite support (30%) represents TiO 2 Occupying Al 2 O 3 30% of the mass.
Example 1
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 0.5g,AgO 1g g sodium alginate 0.0686g.
The TiO 2 /Al 2 O 3 The preparation method of the composite carrier (20%) comprises the following steps:
(1) Mixing 80g of pseudo-boehmite powder with 360g of water, and stirring for 10min at 90 ℃;
(2) 24g of titanium sulfate is added, 100mL of 8% dilute nitric acid is added dropwise, and the reaction is carried out for 8 hours at 90 ℃;
(3) The solution after the reaction is passed through a spray dryer under the ammonia atmosphere to obtain TiO 2 /Al 2 O 3 A composite powder;
(4) The TiO is prepared 2 /Al 2 O 3 Soaking the composite powder in 10% NaOH solution for 30min, washing, drying at 60 ℃, and roasting at 600 ℃ for 5h to obtain the carrier.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 1.36g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water, adding 0.0686g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /O 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 2
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 0.1g,AgO 1g g sodium alginate 0.0686g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 0.272g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water, adding 0.0686g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /N 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 3
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 1g,AgO 1g g sodium alginate 0.0686g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, weighing 2.72g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water, adding 0.0686g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Composite carrier (20%), stirring at room temperature for 1hObtaining a bactericide precursor solution;
s2, dropwise adding 10% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 Stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 4
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 0.5g,AgO 0.5g g sodium alginate 0.0342g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 1.36g of Fe (NO) 3 ) 3 And 0.686g AgNO 3 Dissolving in water, adding 0.0342g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /O 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 5
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 0.5g,AgO 1.5g, sodium alginate 0.1029g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 1.36g of Fe (NO) 3 ) 3 And 2.058g AgNO 3 Dissolving in water, adding 0.1029g alginic acidSodium, stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /O 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 6
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (30%) 10g,FeOOH 0.5g,AgO 1g g sodium alginate 0.0686g.
The TiO 2 /Al 2 O 3 The preparation method of the composite carrier (30%) comprises the following steps:
(1) Mixing 80g of pseudo-boehmite powder with 360g of water, and stirring for 10min at 90 ℃;
(2) 36g of titanium sulfate is added, 100mL of 8% dilute nitric acid is added dropwise, and the reaction is carried out for 8 hours at 90 ℃;
(3) The solution after the reaction is passed through a spray dryer under the ammonia atmosphere to obtain TiO 2 /Al 2 O 3 A composite powder;
(4) The TiO is prepared 2 /Al 2 O 3 Soaking the composite powder in 5% NaOH solution for 30min, washing, drying at 60 ℃, and roasting at 600 ℃ for 5h to obtain the TiO 2 /Al 2 O 3 Composite support (30%).
The embodiment also provides a preparation method of the bactericide, which is the same as that of the embodiment 1.
Example 7
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite carrier (20%) 10g,FeOOH 0.5g,AgO 1g, sodium alginate 0.0137g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 1.36g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water, adding 0.0137g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 2 Stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 8
The embodiment provides a bactericide, which comprises the following components:
TiO 2 carrier 10g,FeOOH 0.5g,AgO 1g, sodium alginate 0.0686g.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, 1.36g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water, adding 0.0686g sodium alginate, and stirring at room temperature for 30min; 10g of TiO is added 2 Stirring for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /O 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Example 9
The embodiment provides a bactericide, which comprises the following components:
TiO 2 /Al 2 O 3 composite support (20%) 10g,FeOOH 0.5g,AgO 1g.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The embodiment also provides a preparation method of the bactericide, which comprises the following steps:
s1, call1.36g of Fe (NO) 3 ) 3 And 1.37g AgNO 3 Dissolving in water; 10g of TiO is added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /N 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Comparative example
The comparative example provides a bactericide which comprises the following components:
TiO 2 /Al 2 O 3 10g of composite carrier (20%), 1g of AgO and 0.0686g of sodium alginate.
The TiO 2 /Al 2 O 3 The preparation of the composite support (20%) was the same as in example 1.
The comparative example also provides a preparation method of the bactericide, which comprises the following steps:
s1, weighing 1.37g of AgNO 3 Dissolving in water, adding 0.0686g sodium alginate, and stirring at room temperature for 30min; a further 10g of TiO was added 2 /Al 2 O 3 Stirring the composite carrier (20%) for 1h at room temperature to obtain a bactericide precursor solution;
s2, dropwise adding a 5% NaOH solution into the bactericide precursor solution, and stirring for 10min;
s3, let in O 3 /O 2 Mixing the above materials, stirring for 30min, filtering, washing, and vacuum drying at 60deg.C for 5 hr.
Sterilization performance test
The bactericides obtained in examples 1 to 9 and comparative examples were subjected to sterilization performance test by the following specific test methods:
and taking circulating system cooling water of Dongguan Dongyang optical research and development limited company as experimental water to perform a sterilization experiment. 200mL of circulating water sample is taken, 8mg of the bactericide prepared above is added, and the amount of heterotrophic bacteria in the circulating water is measured by sampling at regular time, and the result is shown in Table 1.
TABLE 1 sterilizing effect of the sterilizing agent
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A circulating water bactericide, characterized in that the bactericide comprises: the carrier, and AgO and FeOOH loaded on the carrier; wherein the mass of AgO is 6-15% of the mass of the carrier, the mass of FeOOH is 1-10% of the mass of the carrier, and the carrier contains TiO 2 ；
Sodium alginate is also contained in the bactericide, and the mass of the sodium alginate is 3-13% of that of AgO;
the carrier is TiO 2 Supports or TiO 2 /Al 2 O 3 Composite carrier, the TiO 2 /Al 2 O 3 In the composite carrier, tiO 2 The mass is Al 2 O 3 10 to 28 percent of the mass.
2. The biocide of claim 1, wherein the TiO 2 /Al 2 O 3 The preparation method of the composite carrier comprises the following steps:
(1) Mixing an aluminum source with water, stirring, adding a titanium source, adding acid liquor, and reacting at 80-100 ℃ for 7-9 hours to obtain a mixed solution;
(2) Spray drying the mixed solution in ammonia atmosphere to obtain TiO 2 /Al 2 O 3 A composite powder;
(3) The TiO is prepared 2 /Al 2 O 3 Soaking the composite powder in sodium hydroxide solution, washing, drying and roasting to obtain the TiO 2 /Al 2 O 3 And (3) a composite carrier.
3. The biocide of claim 2, wherein the aluminum source is pseudo-boehmite;
the titanium source is at least one of titanium sulfate, titanium nitrate and titanium chloride;
the acid liquor is dilute nitric acid;
the concentration of the sodium hydroxide solution is 1-20%;
the drying temperature in the step (3) is 50-70 ℃; the roasting is carried out for 4 to 6 hours at the temperature of 500 to 700 ℃.
4. A method of preparing a biocide as claimed in any one of claims 1 to 3 comprising the steps of:
s1, adding a carrier into an aqueous solution containing a ferric iron source and a monovalent silver source, and stirring to obtain a bactericide precursor solution;
s2, adding alkali liquor into the bactericide precursor solution, stirring, introducing oxidizing gas, filtering, and drying to obtain the bactericide.
5. The method of claim 4, wherein the ferric source is ferric nitrate;
the monovalent silver source is at least one of silver nitrate and silver ammonia complex;
the alkali liquor is at least one of sodium hydroxide and ammonia water;
the oxidizing gas is O 3 、O 2 、O 3 /O 2 Mixed gas, O 3 /N 2 Mixed gas, O 2 /N 2 Any one of the mixed gases.
6. The method according to claim 4, wherein the oxidizing gas is introduced for 20 to 40 minutes, and the drying is performed at 50 to 70℃for 4 to 6 hours in vacuum.
7. The method according to claim 4, further comprising the step of adding sodium alginate to the aqueous solution and stirring at room temperature for 20 to 40 minutes before adding the carrier; the addition amount of the sodium alginate is 1-10% of the mass of the monovalent silver source.
8. Use of the bactericide according to any one of claims 1 to 3 or the bactericide obtained by the preparation method according to any one of claims 4 to 7 in circulating water.
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