CN104710024B - 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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- CN104710024B CN104710024B CN201310676300.7A CN201310676300A CN104710024B CN 104710024 B CN104710024 B CN 104710024B CN 201310676300 A CN201310676300 A CN 201310676300A CN 104710024 B CN104710024 B CN 104710024B
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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 application of phosphate-free water treatment agent composition and said composition in circulating water cooling treatment.
Background technology
In recirculating cooling water system, fouling, corrosion and the aspect problem of harms of microbe three are primarily present.Anti- locking system knot
Dirt is with corrosion most convenient and effective method is that corrosion inhibiting and descaling agent is added in recirculated cooling water.It is cold that the current country is usually used in circulation
But the formula of water process mostly is phosphine system formula, predominantly containing phosphonate group (- PO3H2) corrosion-mitigation scale-inhibition that is directly connected with carbon atom
Agent, often referred to as organic phospho acid.Compared with the inorganic polyphosphate in early stage phosphorus line formulation, organic phospho acid has good chemistry
Stability, not facile hydrolysis, can higher temperature resistant, the advantages of consumption is little, and have inhibition and scale inhibition dual-use function concurrently.But it is conventional organic
Phosphine can not effectively suppress calcium phosphate scale and zinc dirt, and itself easily forms organic phospho acid dirt.In addition, phosphorus-containing compound is to water body
Pollute and cause body eutrophication problem to make people gradually recognize the importance of control phosphorus-containing compound discharge.World wide
Interior many rivers, lake cause aquatic plants growth out of control because entering substantial amounts of phosphorus, and dissolved oxygen in water exhausts, final water quality
Deteriorate, aquatic animals and plants disappearance.With the raising of environmental consciousness, further strict, many places of China in recent years of environmental regulation
Have begun to limit the use containing phosphorus product, therefore low-phosphorous, phosphate-free water treatment agent exploitation has become study hotspot.
The control of bacterium and algae in recirculating cooling water system, is typically controlled by adding bactericide.Conventional sterilization
Agent is divided into two big class, oxidized form and non-oxidative bactericide.Oxidative bactericide is commonly used because its is cheap, but its
Easily affected and interference by the factor such as pH, organic matter, anti-incrustation corrosion inhibitor in recirculated cooling water, be allowed to bactericidal effect reduction, and
Long-Time Service, microorganism develops immunity to drugs. and bactericidal effect will be also affected, while the series bactericidal agent has stronger oxidisability, will be held
Oxidizable other water treatment agents make it fail；Non-oxidative bactericide does not kill microorganism in water with oxidation, but passes through
The privileged sites for acting on microorganism are allowed to lethal.Therefore, non-oxidative bactericide by pH in recirculated cooling water, organic matter,
The impact and interference of the factors such as anti-incrustation corrosion inhibitor.Non-oxidative bactericide can also be the aid antibacteria agent of oxidative bactericide,
The regular non-oxidative bactericide used in recirculated cooling water, can with the biological clay in strip cycles cooling water system, while
Can prevent microorganism from developing immunity to drugs, scene is typically added using impact, and chemical feeding quantity is larger.Most common of which Non-oxidized is killed
Microbial inoculum has quaternary ammonium salt bactericide and OIT, and quaternary ammonium salt bactericide has preferable instantaneous sterilization effect, but drug effect
Duration is short；OIT instantaneous sterilization effect is poor, typically wants dosing 24h just to start to take effect, and dosage is big, expense
Height, Long-Time Service also has corrosiveness to recirculating cooling water system.Although have now been developed many new non-oxidative bactericides,
Oxidative bactericide can be completely substituted but without a kind of non-oxidative bactericide.And this common several non-oxidative bactericide
From the time of decades is begun to use so far, update speed is slow, and microorganism is easily right during Long-Time Service
It develops immunity to drugs, and needs the concentration for continuing to increase common fungicide to continue to keep preferable bactericidal effect.
The content of the invention
It is an object of the invention to overcome recirculated cooling water is processed using existing water treatment agent during need
Using containing phosphorus component, or the poor defect of the water treatment efficiency obtained containing phosphorus component is not used, there is provided a kind of without phosphorus water
Agent composition and its application.
Generally, gluconate, silicate and borate are nontoxic, inexpensive corrosion inhibiter, will not be to the mankind in use
Any direct or indirect harm is caused with environment, but is not widely used in circulating water cooling treatment, its reason is grape
The dosage that sugar lime is used alone needs is higher, itself is also the nutrient source of microorganism, easily causes a large amount of numerous of microorganism
Grow；It is undesirable that silicate and borate are each used alone corrosion mitigating effect.What Yuan Wanzhong etc. was delivered《Borax-sodium gluconate delays
Erosion agent is in neutral medium to the synergistic corrosion inhibition of carbon steel》Compounded as carbon steel inhibition using sodium gluconate and sodium tetraborate
Agent, only using both corrosion inhibiter, the valid density for using reaches 1000mg/L, and concentration is higher, and formula scale inhibition of do not have
Performance, is used in circulating water cooling treatment defective.
Benzamides bactericide is typically used as crop bactericide, common are metalaxyl, Wakil, M 9834 and first furan
Acid amides.Benzamides bactericide is used as agriculture chemicals fungicide, and bactericidal effect is good, but is rarely used in recirculating cooling water system, mainly
Because this solubility of several medicaments in water is relatively low, the use in circulating water cooling treatment is subject to a definite limitation.
The present inventor's research finds, by by benzamides bactericide, containing sulfonic without phosphorus copolymer and
Selected from gluconate, silicate and the boratory corrosion inhibiter compounding use, benzamides bactericide, containing sulfonic nothing
Phosphorus copolymer and synergy can be played between gluconate, silicate and the boratory corrosion inhibiter, no
The consumption of medicament can be only significantly reduced, but also can be obtained in the case where introducing containing phosphorus component preferably slow
Erosion, scale inhibition and bactericidal effect, so as to complete the present invention.
The invention provides a kind of phosphate-free water treatment agent composition, wherein, said composition contains benzamides bactericide, contains
Sulfonic without phosphorus copolymer and corrosion inhibiter, the corrosion inhibiter is the one kind or many in borate, gluconate and silicate
Kind.
Present invention also offers the application of the phosphate-free water treatment agent composition in treatment of industrial water.
In water process（Particularly circulating water cooling treatment）During, combined using phosphate-free water treatment agent of the present invention
Thing, it is possible to obtain preferable sterilized, inhibition and scale inhibition effect, specifically, scale inhibition performance is higher, corrosion rate relatively slow, sterilizing ability
Stronger and sterilized duration is longer.The 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 will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains 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 bactericide, contains
Sulfonic without phosphorus copolymer and corrosion inhibiter, the corrosion inhibiter is the one kind or many in borate, gluconate and silicate
Kind.
Although by the benzamides bactericide, described containing sulfonic without phosphorus copolymer and selected from borate, grape
The corrosion inhibiter of one or more in sugar lime and silicate is used cooperatively and may be used in water process, but in order to reach
To preferable water treatment efficiency, under preferable case, relative to the corrosion inhibiter of 100 weight portions, the benzamides bactericide
Content be 2-50 weight portions, the content containing sulfonic without phosphorus copolymer be 6-120 weight portions.In the case of more preferably,
Relative to the corrosion inhibiter of 100 weight portions, the content of the benzamides bactericide is 5-20 weight portions, described containing sulfonic group
Without phosphorus copolymer content be 6-100 weight portions.In the case of further preferably, relative to the corrosion inhibiter of 100 weight portions,
The content of the benzamides bactericide is 6-20 weight portions, and the content containing sulfonic without phosphorus copolymer is 8-35 weight
Part.
Phosphate-free water treatment agent composition of the invention, the benzamides bactericide has stronger bactericidal action,
Therefore benzamides bactericide described in the composition of the present invention can be the conventional benzamides bactericide in this area, preferred feelings
Under condition, the benzamides bactericide is one or more in metalaxyl, Wakil, M 9834 and fenfuram, more preferably
For metalaxyl.Wherein, the chemical entitled D of metalaxyl, L-N- (2,6- 3,5-dimethylphenyl)-N- (2- methoxyl group acetyl) alanine first
Ester, its molecular formula is C15H21NO4；Chemical entitled 2- methoxyl groups-N- (2- oxo -1,3- oxazolidine -3- bases) acetyl of Wakil
Amine-n-(2 ', 6 '-dimethyl benzene), its molecular formula is C14H18N2O4；The chemical entitled N- phenylacetyl groups-N-2,6- two of M 9834
Tolyl-DL-Alanine methyl esters, its molecular formula is C20H23NO3；The chemical entitled N- phenylacetyl groups-N-2,6- two of fenfuram
Tolyl-DL-Alanine methyl esters, its molecular formula is C12H11NO2.Further, since solubility of the benzamides bactericide in water
It is relatively low, therefore, more preferably in the case of, the Shi Kexian that makes up a prescription is dissolved with a small amount of ethanol.
Phosphate-free water treatment agent composition of the invention, it is described that there is scale inhibition and dispersion containing sulfonic without phosphorus copolymer
Can, especially when the copolymer is bipolymer and/or terpolymer containing sulfonic group and carboxylic acid group, wherein, institute
State bipolymer and be preferably acrylic acid/2- methyl -2 '-acrylamido propane sulfonic acid copolymer (AA/AMPS), the ternary
Copolymer be preferably acrylic acid/acrylamide/2- methyl -2 '-acrylamido propane sulfonic acid copolymer (AA/AM/AMPS), third
Olefin(e) acid/acrylate/2- methyl -2 '-acrylamido propane sulfonic acid copolymer (AA/ acrylate/AMPS）With acrylic acid/horse
One or more come in acid anhydrides/2- methyl -2 '-acrylamido propane sulfonic acid copolymer (AA/ maleic anhydrides/AMPS), its
In, the acrylate is preferably acrylic acid C1-C8 alkyl or hydroxy alkyl ester, more preferably methyl acrylate (MA), acrylic acid
Ethyl ester (EA) or hydroxypropyl acrylate (HPA).The polymerization initiation system of the copolymer is not phosphorous initiator system, preferably
Sodium pyrosulfite and ammonium persulfate initiator system, the concrete synthesis step of the copolymer is well known to those skilled in the art,
Will not be described here.
Phosphate-free water treatment agent composition of the invention, the borate, gluconate and silicate do not have spy
Do not limit, as long as the conventional corrosion inhibiter for corrosion inhibition being 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 kodalk；Such as described Portugal
Grape sugar lime can be sodium gluconate and/or zinc gluconate；The silicate be preferably sodium metasilicate, anhydrous sodium metasilicate,
One or more in metasilicate pentahydrate sodium and non-hydrate sodium metasilicate.
The phosphate-free water treatment agent composition of the present invention can also contain zinc salt, especially, when the phosphate-free water treatment agent group
Compound process compared with severe corrosive recirculated cooling water when, under preferable case, relative to the corrosion inhibiter of 100 weight portions, institute
The content for stating zinc salt is 2-34 weight portions.The zinc salt is preferably zinc sulfate and/or zinc chloride.
The phosphate-free water treatment agent composition of the present invention can also contain heterocyclic compound, especially, at the without phosphorus water
Agent composition is managed when the industrial circulating cooling water for equipment made of copper is processed, relative to the corrosion inhibiter of 100 weight portions, institute
The content for stating heterocyclic compound is 2-34 weight portions.The heterocyclic compound is preferably mercaptobenzothiazoler and/or BTA.
In the present invention, the phosphate-free water treatment agent composition can also contain water.The phosphate-free water treatment agent composition
In water content can be determined according to the concentration of conventional water treatment agent.When the phosphate-free water treatment agent composition contains water
When, the phosphate-free water treatment agent composition is preferably present in form of an aqueous solutions, and the concentration of the aqueous solution can be water-treated
The valid density of the practical application of the water treatment agent in journey, or the concentration more richer than practical application valid density, and
Corresponding valid density is diluted in actual application.
A preferred embodiment of the invention, the water treatment agent composition is not phosphorous, namely at the water
Reason medicament composition is not comprising conventional phosphorus family corrosion inhibitor and/or phosphorus system corrosion inhibiting and descaling agent.In the preferred embodiment, the water
Treatment agent composition not only can obtain preferable scale inhibition, inhibition and bactericidal effect, and also avoid traditional water process medicine
Agent uses the medicine containing P elements that the defect of environmental pollution is caused as anti-incrustation corrosion inhibitor in a large number.
Present invention also offers application of the above-mentioned phosphate-free water treatment agent composition in water treatment procedure.
In above-mentioned application process, the water that the phosphate-free water treatment agent composition is adapted to process can be various conventional works
Industry recirculated cooling water, especially, it is 100- that the phosphate-free water treatment agent composition is applied to calcium hardness with total alkalinity sum
The process of the medium hardness of 300mg/L and the recirculated cooling water of moderate alkalinity, processing the recirculated cooling water of the water quality need not adjust
PH value；For calcium hardness and total alkalinity sum are the high rigidity and high alkalinity water quality of more than 300mg/L, with phosphate-free water treatment agent
During compositions-treated, to prevent fouling, often first acid adding adjusts pH value, reduces the basicity in water.
In above-mentioned application process, the phosphate-free water treatment agent composition can be with the normal of this area when for water process
Rule valid density is used, and under preferable case, valid density of phosphate-free water treatment agent composition when for water process is 60-
100mg/L, the valid density refers to that relative to pending water the water treatment agent for adding thereto is 60-100mg/L, i.e.,
The quality of the water treatment agent added in per liter of pending water is 60-100mg.When the water that the water treatment agent is the water treatment agent
During solution, the amount of water in the water treatment agent is also included in the 60-100mg for the adding water treatment agents.Wherein, relative to pending
Water, the valid density of the benzamides bactericide is 0.5-6mg/L, the valid density containing sulfonic without phosphorus copolymer
For 2-6mg/L, the valid density of the corrosion inhibiter is 5-40mg/L（It is described when corrosion inhibiter is using silicate and/or borate
Corrosion inhibiter valid density is preferably selected from being scope 5-30mg/L less than normal；When corrosion inhibiter uses gluconate, the inhibition
Agent valid density is preferably selected from being scope 10-40mg/L bigger than normal）.Under preferable case, relative to pending water, the benzoyl
The valid density of amine bactericide is 1.5-4mg/L, and the valid density containing sulfonic without phosphorus copolymer is 3-5mg/L,
The valid density of the corrosion inhibiter is 10-25mg/L（When corrosion inhibiter is using silicate and/or borate, the corrosion inhibiter has
Effect concentration is preferably selected from being scope 10-20mg/L less than normal；When corrosion inhibiter uses gluconate, the corrosion inhibiter is effectively dense
Degree is preferably selected from being scope 15-25mg/L bigger than normal）.Due to there is collaboration between each component in the water treatment agent of the present invention
Effect, therefore when water is processed with the water treatment agent, the valid density of above-mentioned each component is all relatively low.At the without phosphorus water
When reason agent composition also contains zinc salt, the valid density of the zinc salt（With Zn2+Meter）For 0.5-1.5mg/L, when the without phosphorus water process
When agent composition also contains heterocyclic compound, the valid density of the heterocyclic compound is 0.5-1.5mg/L.
In the following Examples and Comparative Examples, calcium carbonate scale performance test, stable zinc salt performance test, rotary hanging plate are hindered rotten
Corrosion test and bactericidal property test are determined respectively according to following methods：
（1）Resistance calcium carbonate scale performance test
Take distilled water and prepare Ca2+Concentration is 600mg/L, basicity is the test water 1 of 600mg/L and pH value 9.0 or so,
The water treatment agent for preparing is added thereto, 10h, residue Ca in sample analysis water are stood in 80 ± 1 DEG C of waters bath with thermostatic control2+It is dense
Degree, while doing blank sample, and calculates scale inhibition performance.
Scale inhibition performance computing formula is：Scale inhibition performance=(C-C0)×100%/(C1-C0)
C：Actual measurement Ca2+Concentration（mg/L）
C0：The Ca of blank sample2+Concentration（mg/L）
C1：Ca in raw water2+Concentration（mg/L）
（2）Stable zinc salt performance test
Take distilled water and prepare Ca2+Concentration is 250mg/L, basicity is 250mg/L, Zn2+It is 9 or so for 5mg/L and pH value
Test water 2, the water treatment agent for preparing is added thereto, and 10h is stood in 80 ± 1 DEG C of waters bath with thermostatic control, in sample analysis water
Remaining Zn2+Concentration, while do blank sample, and calculate resistance zinc rate.
Hindering zinc rate computing formula is：Resistance zinc rate=(C-C0)×100%/(C1-C0)
C：Actual measurement Zn2+Concentration（mg/L）
C0：The Zn of blank sample2+Concentration（mg/L）
C1：Zn in raw water2+Concentration（mg/L）
（3）Rotary hanging plate corrosion test
20# quality carbon steel test pieces are fixed on lacing film instrument, are put in the test water added with water treatment agent（Respectively by table
Test raw water 1 and 3 in 1 is concentrated into 5 times of concentration, and uncomfortable pH value forms test water 3 and 5；Test raw water 2 in table 1 is concentrated
To 4 times of concentration, and adjust pH value to 7.8-8.2 with sulfuric acid, form test water 4）, 40 ± 1 DEG C of steady temperature, holding rotating speed
75rpm rotates 72h, and the weight of test piece, calculates average corrosion rate before and after record test.
Average corrosion rate computing formula is：F=（C×△W）/（A×T×ρ）
C：Computational constant, during with mm/a (millimeter/year) as unit, C=8.76 × 107
△W：The corrosion weight loss (g) of test specimen
A：Area (the cm of test specimen2)
T：Corrosion test time (h)
ρ：Density (the kg/m of material for test3)
（4）Bactericidal property is tested
In the fluid nutrient medium of heterotroph, running water is inoculated with（The volume ratio of culture medium and running water is 20：1）, in 30
Enrichment culture 1 day in DEG C incubator, and continuous transferred species 3 times, this nutrient solution is original strain.Original strain is diluted with running water,
Bacterium solution is obtained after being sufficiently mixed, triangular flask of the 200ml bacterium solutions loaded on 500ml is taken, the phosphate-free water treatment agent combination of the present invention is added
Thing, is placed in 30 DEG C of incubators, in certain intervals sampling monitoring bacterial population, while doing blank sample, and calculates sterilizing rate, sterilizing rate meter
Calculating formula is：Sterilizing rate=(bacterium number of the bacterium number of same time blank sample-same time sample) × 100%/same time is empty
The bacterium number of white sample.
The water quality parameter of the test raw water used in above-mentioned process of the test is as shown in table 1.
Table 1 tests the water quality parameter of raw water
| Water quality | Ca2+ | Total alkalinity | Total hardness | Cl- | SO4 2- | pH | Electrical conductivity | It is total molten solid |
| Test raw water 1 | 79 | 154 | 140 | 15 | 33 | 8.0 | 201 | 281 |
| Test raw water 2 | 270 | 290 | 352 | 66 | 110 | 7.5 | 995 | 706 |
| Test raw water 3 | 22 | 35 | 50 | 7 | 11 | 7.2 | 108 | 84 |
The assay method of water quality is with reference to as follows：
Ca2+（With CaCO3Meter, mg/L）：Reference standard GB/T6910-2006
Total alkalinity（With CaCO3Meter, mg/L）：Reference standard GB/T15451-2006；
Total hardness（With CaCO3Meter, mg/L）：Reference standard GB/T6909-2008；
Cl-（mg/L）：Reference standard GB/T15453-2008；
SO4 2-（mg/L）：Reference standard GB/T14642-2009；
PH value：Reference standard GB/T6920-1986；
Electrical conductivity (μ s/cm)：Reference standard GB/T6908-2008；
It is total molten solid：Reference standard GB/T14415-2007.
Metalaxyl in the following Examples and Comparative Examples, Wakil and M 9834 are purchased from Solution on Chemical Reagents in Shanghai factory；First
Ofurace is purchased from the side Science and Technology Ltd. of Tianjin one；Borate is purchased from Beijing Yili Fine Chemicals Co., Ltd.；Glucose
Hydrochlorate is purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Silicate is purchased from Beijing Chemical Plant；Containing sulfonic without phosphorus copolymerization
Thing is purchased from the strong Yilong Industry Co., Ltd. in Luoyang；Zinc salt is purchased from Beijing chemical reagents corporation；OIT is purchased from Beijing day
Hold up Chemical Co., Ltd.；Strong chlorine oil is purchased from the calm and peaceful water process Co., Ltd in Shandong.It is noted that containing purchased from above company
Sulfonic without phosphorus copolymer and OIT are present in form of an aqueous solutions.
Embodiment 1-14 is used to illustrate the phosphate-free water treatment agent composition of present invention offer.
Embodiment 1
The preparation of water treatment agent：At room temperature, 2.0g metalaxyls are first dissolved in the ethanol of 5mL, then are hydrated with 19g ten
Sodium tetraborate and the AA/AM/AMPS copolymers that 13.4g solid contents are 30 weight % are dissolved in together in deionized water, and stirring is equal
It is even, it is configured to 100g water treatment agent A1.
Embodiment 2
The preparation of water treatment agent：At room temperature, 4g metalaxyls are first dissolved in the ethanol of 5mL, then with 25g gluconic acids
Sodium and the AA/AMPS copolymers that 15.1g solid contents are 30 weight % are dissolved in together in deionized water, are stirred, and are configured to
100g water treatment agent A2.
Embodiment 3
The preparation of water treatment agent：At room temperature, 3g metalaxyls are first dissolved in the ethanol of 10mL, then it is anhydrous with 15g inclined
Sodium metasilicate and the AA/HPA/AMPS copolymers that 16.8g solid contents are 30 weight % are dissolved in together in deionized water, are stirred,
It is configured to 100g water treatment agent A3.
Embodiment 4
The preparation of water treatment agent：At room temperature, 1.5g metalaxyls are first dissolved in the ethanol of 5mL, then with 13g glucose
Sour zinc, 10g sodium metasilicate and the AA/MA/AMPS copolymers that 10.1g solid contents are 30 weight % are dissolved in together in deionized water, are stirred
Mix uniform, be configured to 100g water treatment agent A4.
Embodiment 5
The preparation of water treatment agent：At room temperature, the metalaxyl of 1g is first dissolved in the ethanol of 5mL, then with 5g metasilicic acids
Sodium, the AA/EA/AMPS copolymers that 10.1g solid contents are 30 weight % and the AA/MA/AMPS that 6.7g solid contents are 30 weight % are total to
Polymers is dissolved in together in deionized water, is stirred, and is configured to 100g water treatment agent A5.
Embodiment 6
The preparation of water treatment agent：At room temperature, the metalaxyl of 6g is first dissolved in the ethanol of 10mL, then with 43.4g five
Water sodium tetraborate, 6.6g white vitriols, the AA/ that 6.7g solid contents are 30 weight % maleic anhydrides/AMPS copolymer and 6.7g consolidate
Content is that the AA/HPA/AMPS copolymers of 30 weight % are dissolved in together in deionized water, is stirred, and is configured at 100g water
Reason agent A6.
Embodiment 7
The preparation of water treatment agent：At room temperature, 4.5g metalaxyls are first dissolved in the ethanol of 10mL, then with 18.6g nine
The anhydrous sodium tetraborate of water sodium metasilicate, 10g, 4.4g white vitriols and the AA/AMPS copolymerization that 20.1g solid contents are 30 weight %
Thing is dissolved in together in deionized water, is stirred, and is configured to 100g water treatment agent A7.
Embodiment 8
The preparation of water treatment agent：At room temperature, 1.5g M 9834s and 2g Wakils are first dissolved in the ethanol of 5mL, then
It is molten together with 40g sodium gluconates, 4.4g white vitriols and AA/HPA/AMPS copolymers that 18.4g solid contents are 30 weight %
Solution stirs in deionized water, is configured to 100g water treatment agent A8.
Embodiment 9
The preparation of water treatment agent：At room temperature, 1g metalaxyls and 1g fenfurams are first dissolved in the ethanol of 5mL, then
Dissolve together with 35g zinc gluconates, 2.2g white vitriols and AA/AM/AMPS copolymers that 6.7g solid contents are 30 weight %
In deionized water, stir, be configured to 100g water treatment agent A9.
Embodiment 10
The preparation of water treatment agent：At room temperature, 0.5g metalaxyls are first dissolved in the ethanol of 5mL, then with 10g glucose
Sour sodium and AA/ maleic anhydrides/AMPS copolymer that 8.4g solid contents are 30 weight % are dissolved in together in deionized water, and stirring is equal
It is even, it is configured to 100g water treatment agent A10.
Embodiment 11
Water treatment agent is prepared according to the method for embodiment 1, except for the difference that, adds Wakil to replace metalaxyl, so as to obtain
Water treatment agent A11.
Embodiment 12
Water treatment agent is prepared according to the method for embodiment 2, except for the difference that, adds Wakil to replace metalaxyl, so as to obtain
Water treatment agent A12.
Embodiment 13
Water treatment agent is prepared according to the method for embodiment 1, except for the difference that, adds M 9834 to replace metalaxyl, so as to obtain
Water treatment agent A13.
Embodiment 14
Water treatment agent is prepared according to the method for embodiment 1, except for the difference that, adds fenfuram to replace metalaxyl, so as to
To water treatment agent A14.
Comparative example 1
Water treatment agent is prepared according to the method for embodiment 1, except that, metalaxyl is added without, so as to the water process of system
Agent B1.
Comparative example 2
Water treatment agent is prepared according to the method for embodiment 1, except that, sodium borate decahydrate is added without, so as to make
Water treatment agent B2.
Comparative example 3
Water treatment agent is prepared according to the method for embodiment 1, except that, AA/AM/AMPS copolymers are added without, so as to
The water treatment agent B3 of system.
Comparative example 4
Water treatment agent is prepared according to the method for embodiment 2, except that, add 4.5g active ingredients to be 90 weight %
Strong chlorine oil replaces metalaxyl, so as to the water treatment agent B4 of system.
Comparative example 5
Water treatment agent is prepared according to the method for embodiment 3, except that, add 17.9g active ingredients to be 14 weight %
OIT replaces metalaxyl, so as to the water treatment agent B5 of system.
Test case 1
This test case is used for scale inhibition, inhibition and the bactericidal property of the phosphate-free water treatment agent for illustrating present invention offer.
B1-B5 in water treatment agent A1-A14 and comparative example in above-described embodiment is put into into respectively resistance calcium carbonate scale performance
The test water 1 of test and tested accordingly in stablizing the test water 2 of zinc salt performance test, and by A1-A5, A10-
A14 and B1-B5 put into respectively other A6-A9 in test water 3 and put into respectively in test water 4 and 5 and carry out rotary hanging plate corrosion
Test, wherein, relative to every liter of test water, the dosage of the water treatment agent is 100mg, and result of the test is as shown in table 3.
B1-B5 in water treatment agent A1-A14 and comparative example in above-described embodiment is put into into respectively bactericidal property test
In bacterium solution, wherein, relative to every liter of bacterium solution, the dosage of the water treatment agent is 100mg, and 30 DEG C of incubator is put into after shaking up
In, the bacterial population of sample analysis monitoring in required time, sterilizing rate the results are shown in Table 4.
More than test pending water in, the valid density of each component of water treatment agent used is as shown in table 2.
The valid density of the component of each water treatment agent in the pending water of table 2
The scale inhibitor effect of the water treatment agent of table 3
The bactericidal property result of the test of table 4
Note：Initial bacterium number is 2.1 × 106Individual/mL, cell is indicated without bactericidal action for "/".
Data from table 3,4 can be seen that the present invention phosphate-free water treatment agent composition have preferable scale-inhibiting properties,
Corrosion inhibition and sterilizing ability, are a kind of water treatment agents of excellent performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of phosphate-free water treatment agent composition, it is characterised in that said composition is by benzamides bactericide, containing sulfonic nothing
Phosphorus copolymer, corrosion inhibiter, optional zinc salt, optional heterocyclic compound and optional water composition, the corrosion inhibiter be borate,
One or more in gluconate and silicate；Relative to the corrosion inhibiter of 100 weight portions, the benzamides is sterilized
The content of agent is 2-50 weight portions, and the content containing sulfonic without phosphorus copolymer is 6-120 weight portions；The benzamides
Bactericide is one or more in metalaxyl, Wakil, M 9834 and fenfuram.
2. composition according to claim 1, wherein, relative to the corrosion inhibiter of 100 weight portions, the benzamides
The content of bactericide is 5-20 weight portions, and the content containing sulfonic without phosphorus copolymer is 6-100 weight portions.
3. composition according to claim 2, wherein, relative to the corrosion inhibiter of 100 weight portions, the benzamides
The content of bactericide is 6-20 weight portions, and the content containing sulfonic without phosphorus copolymer is 8-35 weight portions.
4. composition according to claim 1, wherein, the benzamides bactericide is metalaxyl.
5. the composition according to any one in claim 1-3 and 4, wherein, it is described containing sulfonic without phosphorus copolymer
For bipolymer and/or terpolymer.
6. composition according to claim 5, wherein, the bipolymer is acrylic acid/2- methyl -2 '-acryloyl
Amido propane sulfonic acid copolymer, the terpolymer is acrylic acid/acrylamide/2- methyl -2 '-acrylamido propane sulphur
Acid copolymer, acrylic acid/esters/2- methyl -2 '-acrylamido propane sulfonic acid copolymer and acrylic acid/maleic anhydride/
One or more in 2- methyl -2 '-acrylamido propane sulfonic acid copolymer.
7. the composition according to any one in claim 1-4, wherein, the borate be anhydrous sodium tetraborate, ten
One or more in hydration sodium tetraborate, five hydration sodium tetraborates and kodalk, the gluconate is gluconic acid
Sodium and/or zinc gluconate, the silicate is sodium metasilicate, anhydrous sodium metasilicate, metasilicate pentahydrate sodium and non-hydrate sodium metasilicate
In one or more.
8. the composition according to any one in claim 1-4 and 6, wherein, the composition contains zinc salt, relative to
The corrosion inhibiter of 100 weight portions, the content of the zinc salt is 2-34 weight portions.
9. composition according to claim 8, wherein, the zinc salt is zinc sulfate and/or zinc chloride.
10. the composition according to any one in claim 1-4,6 and 9, wherein, the composition contains heterocyclic compound
Thing, relative to the corrosion inhibiter of 100 weight portions, the content of the heterocyclic compound is 2-34 weight portions.
11. compositions according to claim 10, wherein, the heterocyclic compound is mercaptobenzothiazoler and/or benzo
Triazole.
12. compositions according to any one in claim 1-4,6,9 and 11, wherein, the composition is not phosphorous.
Application of the phosphate-free water treatment agent composition in 13. claims 1-12 described in any one in water treatment procedure.
14. applications according to right 13, wherein, relative to pending water, the benzamides bactericide it is effective dense
Spend for 0.5-6mg/L, the valid density containing sulfonic without phosphorus copolymer is 2-6mg/L, the corrosion inhibiter it is effective dense
Spend for 5-40mg/L.
15. applications according to right 14, wherein, relative to pending water, the benzamides bactericide it is effective dense
Spend for 1.5-4mg/L, the valid density containing sulfonic without phosphorus copolymer is 3-5mg/L, the corrosion inhibiter it is effective dense
Spend for 10-25mg/L.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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