CN104710024A - Phosphorus-free water treatment agent composition and application thereof - Google Patents
Phosphorus-free water treatment agent composition and application thereof Download PDFInfo
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- CN104710024A CN104710024A CN201310676300.7A CN201310676300A CN104710024A CN 104710024 A CN104710024 A CN 104710024A CN 201310676300 A CN201310676300 A CN 201310676300A CN 104710024 A CN104710024 A CN 104710024A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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Abstract
The invention discloses a phosphorus-free water treatment agent composition. The composition contains a benzamide bactericide, a sulfonic group-containing phosphorus-free copolymer and a corrosion inhibitor, and the corrosion inhibitor can be one or more of borate, gluconate and silicate. The invention also discloses an application of the phosphorus-free water treatment agent composition in water treatment. A result of evaluation of the scale inhibition, corrosion inhibition and sterilization performances of the phosphorus-free water treatment agent composition in water treatment shows that the phosphorus-free water treatment agent composition has high calcium carbonate scale inhibition rate, high zinc scale inhibition rate, high sterilization rate and low carbon steel sheet corrosion rate on the premise that no phosphorus treatment agents are contained. The phosphorus-free water treatment agent has the advantages of environmental protection and excellent water treatment effect.
Description
Technical field
The present invention relates to a kind of phosphate-free water treatment agent composition and the application of said composition in circulating water cooling treatment.
Background technology
In recirculating cooling water system, mainly there is fouling, corrosion and harms of microbe three aspect problem.Prevent scaling and corrosion most convenient and effective means adds corrosion inhibiting and descaling agent in recirculated cooling water.The domestic formula being usually used in circulating water cooling treatment mostly is phosphine system formula at present, is mainly containing phosphonate group (-PO
3h
2) the direct corrosion inhibiting and descaling agent be connected with carbon atom, be often referred to as organic phospho acid.Compared with the inorganic polyphosphate in early stage phosphorus line formulation, organic phospho acid have good chemical stability, not facile hydrolysis, can the advantage such as higher temperature resistant, consumption be little, and have inhibition and scale inhibition dual-use function concurrently.But conventional organic phosphine can not suppress calcium phosphate scale and zinc dirt effectively, and itself is easily formed with machine phosphonic acid dirt.In addition, P contained compound to the pollution of water body and cause body eutrophication problem make people recognize gradually control P contained compound discharge importance.In world wide, a lot of river, lake cause aquatic plants growth out of control because enter a large amount of phosphorus, and dissolved oxygen in water exhausts, final water quality deterioration, and aquatic animals and plants disappeares.Along with the raising of environmental consciousness, environmental regulation further strict, the many places of China have started to limit the use containing phosphorus product in recent years, and therefore exploitation that is low-phosphorous, phosphate-free water treatment agent becomes study hotspot.
The control of bacterium and algae in recirculating cooling water system, generally by adding sterilant to control.Conventional sterilant is divided into two large class, oxidized form and non-oxidative bactericides.Oxidative bactericide is commonly used because it is cheap, but it is subject to impact and the interference of the factors such as pH in recirculated cooling water, organism, anti-incrustation corrosion inhibitor, make it sterilization effect to reduce, and life-time service, microorganism develops immunity to drugs. also will affect sterilization effect, this series bactericidal agent has stronger oxidisability simultaneously, and easily other water conditioners of oxidation make it lose efficacy; Non-oxidative bactericide does not kill microorganism in water with oxygenizement, but makes it lethal by the privileged sites acting on microorganism.Therefore, non-oxidative bactericide is not by impact and the interference of the factors such as pH, organism, anti-incrustation corrosion inhibitor in recirculated cooling water.Non-oxidative bactericide can also be the aid antibacteria agent of oxidative bactericide, regularly in recirculated cooling water, use non-oxidative bactericide, can biological clay in strip cycles cooling water system, can prevent microorganism from developing immunity to drugs simultaneously, on-the-spot general employing impact adds, and chemical feeding quantity is larger.Wherein modal non-oxidative bactericide has quaternary ammonium salt sterilant and isothiazolinone, and quaternary ammonium salt sterilant has good instantaneous sterilization effect, but duration of efficacy is short; Isothiazolinone instantaneous sterilization effect is poor, generally wants dosing 24h just to start to take effect, and dosage is large, and costly, life-time service also has corrosive nature to recirculating cooling water system.Although have now been developed a lot of novel non-oxidative bactericide, also do not have a kind of non-oxidative bactericide can substitute oxidative bactericide completely.And this common several non-oxidative bactericide is from bringing into use the time of existing decades so far, update speed is slow, in life-time service process, microorganism easily develops immunity to drugs to it, needs the working concentration continuing to increase common fungicide could continue to keep good sterilization effect.
Summary of the invention
The object of the invention is to overcome in the process adopting existing water conditioner to process recirculated cooling water needs to use containing phosphorus component, or do not use the defect that the water treatment efficiency that obtains containing phosphorus component is poor, a kind of phosphate-free water treatment agent composition and application thereof are provided.
Usually, gluconate, silicate and borate are nontoxic, inexpensive inhibiter, any harm directly or indirectly can not be caused to the mankind and environment in using, but be not all widely used in circulating water cooling treatment, it is higher that its reason is that gluconate is used alone the dosage of needs, itself be also the nutrition source of microorganism, easily cause the amount reproduction of microorganism; It is undesirable that silicate and borate are used alone corrosion mitigating effect separately." borax-Sunmorl N 60S inhibiter in neutral medium to the synergistic corrosion inhibition of carbon steel " that Yuan Wanzhong etc. deliver using Sunmorl N 60S and sodium tetraborate composite as carbon steel corrosion inhibitor, only use this two kinds of inhibiter, the effective concentration used reaches 1000mg/L, concentration is higher, and formula does not have scale-inhibiting properties, is used in circulating water cooling treatment defectiveness.
Benzamides sterilant is typically used as crop bactericide, common are metaxanin, Wakil, M 9834 and fenfuram.Benzamides sterilant is used as agricultural bactericide, and sterilization effect is good, but is rarely used in recirculating cooling water system, and mainly because the solubleness of this several medicament in water is lower, the use in circulating water cooling treatment is subject to a definite limitation.
The present inventor studies discovery, by by benzamides sterilant, containing sulfonic without phosphorus multipolymer and be selected from gluconate, silicate and the composite use of boratory described inhibiter, benzamides sterilant, containing sulfonic without phosphorus multipolymer and be selected from gluconate, can synergy be played between silicate and boratory described inhibiter, significantly can not only reduce the consumption of medicament, but also good inhibition, scale inhibition and sterilization effect can be obtained when not needing introducing containing when phosphorus component, thus complete the present invention.
The invention provides a kind of phosphate-free water treatment agent composition, wherein, said composition contains benzamides sterilant, containing sulfonic without phosphorus multipolymer and inhibiter, described inhibiter is one or more in borate, gluconate and silicate.
Present invention also offers this application of phosphate-free water treatment agent composition in treatment of industrial water.
In water treatment (particularly circulating water cooling treatment) process, adopt phosphate-free water treatment agent composition of the present invention, good sterilization, inhibition and scale inhibition effect can be obtained, particularly, scale inhibition performance is higher, erosion rate is comparatively slow, sterilizing ability is comparatively strong and the sterilization time length is longer.Scale inhibition effect major embodiment of the present invention is in suppression calcium carbonate scale and dispersion zinc salt.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of phosphate-free water treatment agent composition, wherein, said composition contains benzamides sterilant, containing sulfonic without phosphorus multipolymer and inhibiter, described inhibiter is one or more in borate, gluconate and silicate.
Although by described benzamides sterilant, described containing sulfonic without phosphorus multipolymer and one or more the described inhibiter that is selected from borate, gluconate and silicate with the use of just may be used in water treatment, but in order to reach good water treatment efficiency, under preferable case, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 2-50 weight part, and the described content containing sulfonic without phosphorus multipolymer is 6-120 weight part.More preferably in situation, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 5-20 weight part, and the described content containing sulfonic without phosphorus multipolymer is 6-100 weight part.Under further preferable case, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 6-20 weight part, and the described content containing sulfonic without phosphorus multipolymer is 8-35 weight part.
According to phosphate-free water treatment agent composition of the present invention, described benzamides sterilant has stronger germicidal action, therefore benzamides sterilant described in composition of the present invention can be the benzamides sterilant of this area routine, under preferable case, described benzamides sterilant is one or more in metaxanin, Wakil, M 9834 and fenfuram, is more preferably metaxanin.Wherein, the chemistry of metaxanin is called D, and L-N-(2,6-3,5-dimethylphenyl)-N-(2-methoxyl group acetyl) alanine methyl ester, its molecular formula is C
15h
21nO
4; The chemistry of Wakil is called 2-methoxyl group-N-(2-oxo-1,3-oxazoles alkane-3-base) ethanamide-N-(2 ', 6 '-dimethyl benzene), and its molecular formula is C
14h
18n
2o
4; The chemistry of M 9834 is called N-phenylacetyl-N-2,6-xylyl-DL-Alanine methyl esters, and its molecular formula is C
20h
23nO
3; The chemistry of fenfuram is called N-phenylacetyl-N-2,6-xylyl-DL-Alanine methyl esters, and its molecular formula is C
12h
11nO
2.In addition, because the solubleness of benzamides sterilant in water is lower, therefore, more preferably in situation, a small amount of dissolve with ethanol of the Shi Kexian that makes up a prescription.
According to phosphate-free water treatment agent composition of the present invention, described have scale inhibition and dispersion performance containing sulfonic without phosphorus multipolymer, especially when this multipolymer be copolymer containing sulfonic group and carboxylic acid group and/or terpolymer time, wherein, described copolymer is preferably vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (AA/AMPS), described terpolymer is preferably acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (AA/AM/AMPS), one or more in acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (AA/ acrylate/AMPS) and vinylformic acid/maleic anhydride/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (AA/ maleic anhydride/AMPS), wherein, described acrylate is preferably vinylformic acid C1-C8 alkyl or hydroxy alkyl ester, be more preferably methyl acrylate (MA), ethyl propenoate (EA) or Propylene glycol monoacrylate (HPA).The polymerization initiation of described multipolymer is not phosphorous initiator system, and be preferably Sodium Pyrosulfite and ammonium persulphate initiator system, the concrete synthesis step of described multipolymer is well known to those skilled in the art, and does not repeat them here.
According to phosphate-free water treatment agent composition of the present invention, described borate, gluconate and silicate are not particularly limited, as long as be the inhibiter of the routine for corrosion inhibition well known in the art.Such as described borate can be one or more in anhydrous sodium tetraborate, sodium borate decahydrate, five hydration sodium tetraborates and sodium metaborate; Such as described gluconate can be Sunmorl N 60S and/or Zinc Gluconate; Described silicate be preferably in water glass, anhydrous sodium metasilicate, metasilicate pentahydrate sodium and non-hydrate sodium metasilicate one or more.
Phosphate-free water treatment agent composition of the present invention can also contain zinc salt, especially, when described phosphate-free water treatment agent composition is when processing the recirculated cooling water compared with severe corrosive, under preferable case, relative to the described inhibiter of 100 weight parts, the content of described zinc salt is 2-34 weight part.This zinc salt is preferably zinc sulfate and/or zinc chloride.
Phosphate-free water treatment agent composition of the present invention can also contain heterogeneous ring compound, especially, when described phosphate-free water treatment agent composition is in the industrial circulating cooling water process for equipment made of copper, relative to the described inhibiter of 100 weight parts, the content of described heterogeneous ring compound is 2-34 weight part.This heterogeneous ring compound is preferably mercaptobenzothiazole and/or benzotriazole.
In the present invention, described phosphate-free water treatment agent composition can also contain water.Water-content in described phosphate-free water treatment agent composition can be determined according to the concentration of the water conditioner of routine.When described phosphate-free water treatment agent composition contains water, described phosphate-free water treatment agent composition preferably exists in form of an aqueous solutions, the concentration of this aqueous solution can be the effective concentration of the practical application of the water conditioner in water treatment procedure, also can be the concentration denseer than practical application effective concentration, and in actual application, be diluted to corresponding effective concentration.
A preferred embodiment of the invention, described water treatment agent composition is not phosphorous, and namely described water treatment agent composition does not comprise conventional phosphorus family corrosion inhibitor and/or phosphorus system corrosion inhibiting and descaling agent yet.In this preferred implementation, this water treatment agent composition not only can obtain good scale inhibition, inhibition and sterilization effect, but also avoids traditional water treatment agent and use the medicine containing phosphoric to cause the defect of environmental pollution as anti-incrustation corrosion inhibitor in a large number.
Present invention also offers the application of above-mentioned phosphate-free water treatment agent composition in water treatment procedure.
In above-mentioned application process, the water that described phosphate-free water treatment agent composition is applicable to processing can be the industrial circulating cooling water of various routine, especially, described phosphate-free water treatment agent composition is applicable to the process that calcium hardness and total alkalinity sum are the medium hardness of 100-300mg/L and the recirculated cooling water of moderate alkalinity, and the recirculated cooling water processing this water quality does not need adjust pH; For high rigidity and high alkalinity water quality that calcium hardness and total alkalinity sum are more than 300mg/L, when by phosphate-free water treatment agent compositions-treated, for preventing fouling, often first acid adding adjust pH, reduces the basicity in water.
In above-mentioned application process, described phosphate-free water treatment agent composition is for using with the conventional effective concentration of this area during water treatment, under preferable case, described phosphate-free water treatment agent composition is being 60-100mg/L for effective concentration during water treatment, this effective concentration refers to relative to pending water, this water conditioner added wherein is 60-100mg/L, and the quality of the water conditioner namely added in often liter of pending water is 60-100mg.When this water conditioner is the aqueous solution of described water conditioner, in this water conditioner of the 60-100mg added, also comprise the amount of water in this water conditioner.Wherein, relative to pending water, the effective concentration of described benzamides sterilant is 0.5-6mg/L, the described effective concentration containing sulfonic without phosphorus multipolymer is 2-6mg/L, the effective concentration of described inhibiter is that 5-40mg/L(works as inhibiter when using silicate and/or borate, and it is scope 5-30mg/L less than normal that described inhibiter effective concentration is preferably selected from; When inhibiter uses gluconate, it is scope 10-40mg/L bigger than normal that described inhibiter effective concentration is preferably selected from).Under preferable case, relative to pending water, the effective concentration of described benzamides sterilant is 1.5-4mg/L, the described effective concentration containing sulfonic without phosphorus multipolymer is 3-5mg/L, the effective concentration of described inhibiter is that 10-25mg/L(works as inhibiter when using silicate and/or borate, and it is scope 10-20mg/L less than normal that described inhibiter effective concentration is preferably selected from; When inhibiter uses gluconate, it is scope 15-25mg/L bigger than normal that described inhibiter effective concentration is preferably selected from).Owing to having synergy between each component in water conditioner of the present invention, therefore when with this water conditioner process water, the effective concentration of each component above-mentioned is all relatively on the low side.When this phosphate-free water treatment agent composition is also containing zinc salt, the effective concentration of this zinc salt is (with Zn
2+meter) be 0.5-1.5mg/L, when this phosphate-free water treatment agent composition is also containing heterogeneous ring compound, the effective concentration of this heterogeneous ring compound is 0.5-1.5mg/L.
In the following Examples and Comparative Examples, hinder calcium carbonate scale performance test, stablize zinc salt performance test, rotary hanging plate corrosion test and bactericidal property and test and measure according to following methods respectively:
(1) calcium carbonate scale performance test is hindered
Get distilled water preparation Ca
2+concentration is 600mg/L, basicity is 600mg/L and pH value in the test water 1 of about 9.0, the water conditioner prepared is added wherein, in 80 ± 1 DEG C of waters bath with thermostatic control leave standstill 10h, remain Ca in sampling analysis water
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0) × 100%/(C
1-C
0)
C: actual measurement Ca
2+concentration (mg/L)
C
0: the Ca of blank sample
2+concentration (mg/L)
C
1: the Ca in former water
2+concentration (mg/L)
(2) zinc salt performance test is stablized
Get distilled water preparation Ca
2+concentration is 250mg/L, basicity is 250mg/L, Zn
2+for the test water 2 that 5mg/L and pH value are about 9, the water conditioner prepared is added wherein, in 80 ± 1 DEG C of waters bath with thermostatic control, leave standstill 10h, in sampling analysis water, remain Zn
2+concentration, make blank sample simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C
0) × 100%/(C
1-C
0)
C: actual measurement Zn
2+concentration (mg/L)
C
0: the Zn of blank sample
2+concentration (mg/L)
C
1: the Zn in former water
2+concentration (mg/L)
(3) rotary hanging plate corrosion test
The test piece of 20# qualitative carbon steel is fixed on lacing film instrument, puts into the test water being added with water conditioner and (respectively former for the test of table 1 water 1 and 3 is concentrated into 5 times of concentration, not adjust pHs, forms test water 3 and 5; The former water 2 of test in table 1 is concentrated into 4 times of concentration, and with sulfuric acid adjust pH to 7.8-8.2, forms test water 4), steady temperature 40 ± 1 DEG C, keeps rotating speed 75rpm to rotate 72h, and the weight of test piece before and after record test, calculates average corrosion rate.
Average corrosion rate calculation formula is: F=(C × △ W)/(A × T × ρ)
C: computational constant, during with mm/a (millimeter/year) for unit, C=8.76 × 10
7
△ W: the corrosion weight loss (g) of test specimen
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
(4) bactericidal property test
In the liquid nutrient medium of heterotrophic bacterium, inoculation tap water (volume ratio of substratum and tap water is 20:1), enrichment culture 1 day in 30 DEG C of incubators, and continuous transferred species 3 times, this nutrient solution is original strain.Original strain is diluted with tap water, bacterium liquid is obtained after abundant mixing, get the triangular flask that 200ml bacterium liquid is loaded on 500ml, add phosphate-free water treatment agent composition of the present invention, be placed in 30 DEG C of incubators, in certain intervals sampling monitoring bacterial count, make blank sample simultaneously, and calculating sterilizing rate, sterilizing rate calculation formula is: the bacterium number of sterilizing rate=(the bacterium number of the bacterium number-same time sample of blank sample of same time) × 100%/same time blank sample.
The water quality parameter of the former water of the test used in above-mentioned process of the test is as shown in table 1.
The water quality parameter of former water tested by table 1
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl- | SO 4 2- | pH | Specific conductivity | Total molten solid |
| Test former water 1 | 79 | 154 | 140 | 15 | 33 | 8.0 | 201 | 281 |
| Test former water 2 | 270 | 290 | 352 | 66 | 110 | 7.5 | 995 | 706 |
| Test former water 3 | 22 | 35 | 50 | 7 | 11 | 7.2 | 108 | 84 |
The measuring method of water quality is with reference to as follows:
Ca
2+(with CaCO
3meter, mg/L): reference standard GB/T6910-2006
Total alkalinity is (with CaCO
3meter, mg/L): reference standard GB/T15451-2006;
Total hardness is (with CaCO
3meter, mg/L): reference standard GB/T6909-2008;
Cl-(mg/L): reference standard GB/T15453-2008;
SO
4 2-(mg/L): reference standard GB/T14642-2009;
PH value: reference standard GB/T6920-1986;
Specific conductivity (μ s/cm): reference standard GB/T6908-2008;
Total molten solid: reference standard GB/T14415-2007.
Metaxanin in the following Examples and Comparative Examples, Wakil and M 9834 are all purchased from Solution on Chemical Reagents in Shanghai factory; Fenfuram is purchased from Tianjin one side Science and Technology Ltd.; Borate is all purchased from Beijing Yili Fine Chemicals Co., Ltd.; Gluconate is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Silicate is all purchased from Beijing Chemical Plant; Containing sulfonic without phosphorus multipolymer all purchased from the strong Yilong Industry Co., Ltd. in Luoyang; Zinc salt is all purchased from Beijing chemical reagents corporation; Isothiazolinone is purchased from Beijing Tianqing Chemical Co., Ltd.; Strong chlorine oil is purchased from the calm and peaceful water treatment company limited in Shandong.It is worth mentioning that, existing all in form of an aqueous solutions containing sulfonic without phosphorus multipolymer and isothiazolinone purchased from above company.
Embodiment 1-14 is for illustration of described phosphate-free water treatment agent composition provided by the invention.
Embodiment 1
The preparation of water conditioner: at room temperature, 2.0g metaxanin is first dissolved in the ethanol of 5mL, be dissolved in deionized water together with the AA/AM/AMPS multipolymer being 30 % by weight with 19g sodium borate decahydrate and 13.4g solid content again, stir, be mixed with 100g water conditioner A1.
Embodiment 2
The preparation of water conditioner: at room temperature, 4g metaxanin is first dissolved in the ethanol of 5mL, be dissolved in deionized water together with the AA/AMPS multipolymer being 30 % by weight with 25g Sunmorl N 60S and 15.1g solid content again, stir, be mixed with 100g water conditioner A2.
Embodiment 3
The preparation of water conditioner: at room temperature, 3g metaxanin is first dissolved in the ethanol of 10mL, be dissolved in deionized water together with the AA/HPA/AMPS multipolymer being 30 % by weight with 15g anhydrous sodium metasilicate and 16.8g solid content again, stir, be mixed with 100g water conditioner A3.
Embodiment 4
The preparation of water conditioner: at room temperature, 1.5g metaxanin is first dissolved in the ethanol of 5mL, be dissolved in deionized water together with the AA/MA/AMPS multipolymer being 30 % by weight with 13g Zinc Gluconate, 10g water glass and 10.1g solid content again, stir, be mixed with 100g water conditioner A4.
Embodiment 5
The preparation of water conditioner: at room temperature, the metaxanin of 1g is first dissolved in the ethanol of 5mL, with 5g Starso, 10.1g solid content be again 30 % by weight AA/EA/AMPS multipolymer and 6.7g solid content be 30 % by weight AA/MA/AMPS multipolymer together be dissolved in deionized water, stir, be mixed with 100g water conditioner A5.
Embodiment 6
The preparation of water conditioner: at room temperature, the metaxanin of 6g is first dissolved in the ethanol of 10mL, with 43.4g five water sodium tetraborate, 6.6g Zinc Sulphate Heptahydrate, 6.7g solid content be again 30 % by weight AA/ maleic anhydride/AMPS copolymer and 6.7g solid content be 30 % by weight AA/HPA/AMPS multipolymer together be dissolved in deionized water, stir, be mixed with 100g water conditioner A6.
Embodiment 7
The preparation of water conditioner: at room temperature, 4.5g metaxanin is first dissolved in the ethanol of 10mL, be dissolved in deionized water together with the AA/AMPS multipolymer being 30 % by weight with 18.6g non-hydrate sodium metasilicate, the anhydrous sodium tetraborate of 10g, 4.4g Zinc Sulphate Heptahydrate and 20.1g solid content again, stir, be mixed with 100g water conditioner A7.
Embodiment 8
The preparation of water conditioner: at room temperature, 1.5g M 9834 and 2g Wakil are first dissolved in the ethanol of 5mL, be dissolved in deionized water together with the AA/HPA/AMPS multipolymer being 30 % by weight with 40g Sunmorl N 60S, 4.4g Zinc Sulphate Heptahydrate and 18.4g solid content again, stir, be mixed with 100g water conditioner A8.
Embodiment 9
The preparation of water conditioner: at room temperature, 1g metaxanin and 1g fenfuram are first dissolved in the ethanol of 5mL, be dissolved in deionized water together with the AA/AM/AMPS multipolymer being 30 % by weight with 35g Zinc Gluconate, 2.2g Zinc Sulphate Heptahydrate and 6.7g solid content again, stir, be mixed with 100g water conditioner A9.
Embodiment 10
The preparation of water conditioner: at room temperature, 0.5g metaxanin is first dissolved in the ethanol of 5mL, with 10g Sunmorl N 60S and 8.4g solid content be again 30 % by weight AA/ maleic anhydride/AMPS copolymer together be dissolved in deionized water, stir, be mixed with 100g water conditioner A10.
Embodiment 11
Method according to embodiment 1 prepares water conditioner, unlike, add Wakil and replace metaxanin, thus obtain water conditioner A11.
Embodiment 12
Method according to embodiment 2 prepares water conditioner, unlike, add Wakil and replace metaxanin, thus obtain water conditioner A12.
Embodiment 13
Method according to embodiment 1 prepares water conditioner, unlike, add M 9834 and replace metaxanin, thus obtain water conditioner A13.
Embodiment 14
Method according to embodiment 1 prepares water conditioner, unlike, add fenfuram and replace metaxanin, thus obtain water conditioner A14.
Comparative example 1
Method according to embodiment 1 prepares water conditioner, and difference is, does not add metaxanin, thus the water conditioner B1 of system.
Comparative example 2
Method according to embodiment 1 prepares water conditioner, and difference is, does not add sodium borate decahydrate, thus the water conditioner B2 of system.
Comparative example 3
Method according to embodiment 1 prepares water conditioner, and difference is, does not add AA/AM/AMPS multipolymer, thus the water conditioner B3 of system.
Comparative example 4
Method according to embodiment 2 prepares water conditioner, and difference is, adds the strong chlorine oil replacement metaxanin that 4.5g effective constituent is 90 % by weight, thus the water conditioner B4 of system.
Comparative example 5
Method according to embodiment 3 prepares water conditioner, and difference is, adds the isothiazolinone replacement metaxanin that 17.9g effective constituent is 14 % by weight, thus the water conditioner B5 of system.
Test case 1
This test case is for illustration of the scale inhibition of phosphate-free water treatment agent provided by the invention, inhibition and bactericidal property.
Water conditioner A1-A14 in above-described embodiment and the B1-B5 in comparative example is dropped into respectively in the test water 1 of resistance calcium carbonate scale performance test and the test water 2 of stable zinc salt performance test and test accordingly, and A1-A5, A10-A14 and B1-B5 dropped into respectively other A6-A9 in test water 3 and drop into respectively in test water 4 and 5 and carry out rotary hanging plate corrosion test, wherein, relative to often liter of test water, the dosage of described water conditioner is 100mg, and test-results is as shown in table 3.
Water conditioner A1-A14 in above-described embodiment and the B1-B5 in comparative example is dropped into respectively in the bacterium liquid of bactericidal property test, wherein, relative to often liter of bacterium liquid, the dosage of described water conditioner is 100mg, the insulation can of 30 DEG C is put into after shaking up, the bacterial count of sampling analysis monitoring in required time, sterilizing rate the results are shown in Table 4.
In the pending water more than tested, the effective concentration of each component of water conditioner used is as shown in table 2.
The effective concentration of the component of each water conditioner in the water that table 2 is pending
The scale inhibitor effect of table 3 water conditioner
Table 4 bactericidal property test-results
Note: starter bacteria number is 2.1 × 10
6individual/mL, cell is indicating without germicidal action of "/".
Data as can be seen from table 3,4, phosphate-free water treatment agent composition of the present invention has good scale-inhibiting properties, corrosion inhibition and sterilizing ability, is a kind of water conditioner of excellent performance.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. a phosphate-free water treatment agent composition, is characterized in that, said composition contains benzamides sterilant, containing sulfonic without phosphorus multipolymer and inhibiter, and described inhibiter is one or more in borate, gluconate and silicate.
2. composition according to claim 1, wherein, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 2-50 weight part, and the described content containing sulfonic without phosphorus multipolymer is 6-120 weight part;
Preferably, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 5-20 weight part, and the described content containing sulfonic without phosphorus multipolymer is 6-100 weight part;
More preferably, relative to the described inhibiter of 100 weight parts, the content of described benzamides sterilant is 6-20 weight part, and the described content containing sulfonic without phosphorus multipolymer is 8-35 weight part.
3. composition according to claim 1 and 2, wherein, described benzamides sterilant is one or more in metaxanin, Wakil, M 9834 and fenfuram, is preferably metaxanin.
4. according to the composition in claim 1-3 described in any one, wherein, described is copolymer and/or terpolymer containing sulfonic without phosphorus multipolymer.
5. composition according to claim 4, wherein, described copolymer is vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, and described terpolymer is one or more in acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/maleic anhydride/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.
6. according to the composition in claim 1-3 described in any one, wherein, described borate is one or more in anhydrous sodium tetraborate, sodium borate decahydrate, five hydration sodium tetraborates and sodium metaborate, described gluconate is Sunmorl N 60S and/or Zinc Gluconate, and described silicate is one or more in water glass, anhydrous sodium metasilicate, metasilicate pentahydrate sodium and non-hydrate sodium metasilicate.
7. according to the composition in claim 1-6 described in any one, wherein, described composition is also containing zinc salt, and relative to the described inhibiter of 100 weight parts, the content of described zinc salt is 2-34 weight part.
8. according to the composition that claim 7 is stated, wherein, described zinc salt is zinc sulfate and/or zinc chloride.
9. according to the composition in claim 1-6 described in any one, wherein, described composition is also containing heterogeneous ring compound, and relative to the described inhibiter of 100 weight parts, the content of described heterogeneous ring compound is 2-34 weight part.
10. composition according to claim 9, wherein, described heterogeneous ring compound is mercaptobenzothiazole and/or benzotriazole.
11. according to the composition in claim 1-10 described in any one, and wherein, described composition is not phosphorous.
The application of phosphate-free water treatment agent composition in water treatment procedure in 12. claim 1-11 described in any one.
13. application according to right 12, wherein, relative to pending water, the effective concentration of described benzamides sterilant is 0.5-6mg/L, the described effective concentration containing sulfonic without phosphorus multipolymer is 2-6mg/L, and the effective concentration of described inhibiter is 5-40mg/L;
Preferably, relative to pending water, the effective concentration of described benzamides sterilant is 1.5-4mg/L, and the described effective concentration containing sulfonic without phosphorus multipolymer is 3-5mg/L, and the effective concentration of described inhibiter is 10-25mg/L.
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| CN105060511A (en) * | 2015-08-02 | 2015-11-18 | 宁波保税区维迪克环保科技有限公司 | Phosphorus-free corrosion and scale inhibitor for water treatment, and preparation method thereof |
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| CN101647435A (en) * | 2009-07-21 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Synthetical sterilization composition |
| CN101781027A (en) * | 2010-02-09 | 2010-07-21 | 南京工大开元化学有限公司 | High-efficiency non-phosphate corrosion and scale inhibiting dispersing agent and preparation method and application thereof |
| CN102079585A (en) * | 2009-11-26 | 2011-06-01 | 沈阳工业大学 | High-efficiency broad-spectrum water quality stabilizer |
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| CN101647435A (en) * | 2009-07-21 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Synthetical sterilization composition |
| CN102079585A (en) * | 2009-11-26 | 2011-06-01 | 沈阳工业大学 | High-efficiency broad-spectrum water quality stabilizer |
| CN101781027A (en) * | 2010-02-09 | 2010-07-21 | 南京工大开元化学有限公司 | High-efficiency non-phosphate corrosion and scale inhibiting dispersing agent and preparation method and application thereof |
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| CN105060511A (en) * | 2015-08-02 | 2015-11-18 | 宁波保税区维迪克环保科技有限公司 | Phosphorus-free corrosion and scale inhibitor for water treatment, and preparation method thereof |
| CN105060511B (en) * | 2015-08-02 | 2017-10-10 | 广州市鑫川工程技术开发公司 | A kind of water process phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
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