CN1345696A - Multi-function water treatment agent for circulating water cooling system - Google Patents
Multi-function water treatment agent for circulating water cooling system Download PDFInfo
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- CN1345696A CN1345696A CN 00124998 CN00124998A CN1345696A CN 1345696 A CN1345696 A CN 1345696A CN 00124998 CN00124998 CN 00124998 CN 00124998 A CN00124998 A CN 00124998A CN 1345696 A CN1345696 A CN 1345696A
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- treating agent
- cooling water
- multifunctional
- recirculating cooling
- water system
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Abstract
The present invention provides a multifunctional water treatment agent for circulation cooling water system. Said water treatment agent is made up by using N,N-di(phosphonomethyl) asparagic acid and one or several kinds of substances selected from 1-hydroxy-1,1-diphosphonoethane, 1-hydroxy-1-phosphonoacetic acid, 2-phosphonate butane-1,2,4-tricarboxyl, polyphosphonocarboxylic acid, acrylate/methyl acrylate bipolymer, acrylate/methyl acrylate/ethyl acrylate tripolymer and sulfonated styrene/maleic anhydride bipolymer and ZnCl2 through the process of compounding and mixing. Said invented product is simple in use, convenient, multifunctional and good in effect.
Description
The present invention relates to a kind of multifunctional water treating agent that is used for recirculating cooling water system.More particularly, the present invention relates to a kind ofly can to clean simultaneously to recirculating cooling water system equipment, the multifunctional water treating agent of pre-film, scale inhibition, inhibition.
As everyone knows, the water in the recirculating cooling water system can produce fouling, breed bacteria under the long-term operation situation, and can etching apparatus, causes the infringement of equipment even scraps.For assurance equipment runs well, must adding under the regular situation play the various medicaments of scale inhibition, inhibition, germicidal action respectively, before using new installation or when shutting down maintenance, also need to add respectively clean, film medicament in advance.Owing to still do not have to play simultaneously the multipurpose agent of cleaning, pre-film, scale inhibition, inhibition in the prior art, so can only carry out dosing respectively separately at present.There are many problems in the medicament of single effect, owing to need add different medicaments respectively, and each medicament is to the requirement difference of medicine machine as 1., therefore, the above medicine machine of two covers will be arranged at least, increased facility investment undoubtedly, loaded down with trivial details operation has also caused the waste of human and material resources; 2. owing to have the synergistic effect problem between the various medicaments, determine to add that will to study medicament before the dose be mutual synergy or cancel each other, otherwise can't determine that each medicament is used in combination the actual performance degree of back drug effect, but the synergistic effect problem of research medicament need drop into a lot of energy, do a lot of tests, bring very big inconvenience to the human consumer undoubtedly; 3. to add dose than multipurpose agent big because special agent adds dose, and such water discharging back can pollute environment, or the like.Along with the develop rapidly of industry and the raising of environmental requirement, people have proposed requirements at the higher level to water conditioner, therefore, need a kind of water conditioner with multiple function that can overcome above-mentioned defective of research.
So, the purpose of this invention is to provide a kind of multifunctional water treating agent that can play cleaning, pre-film, scale inhibition, corrosion inhibition simultaneously.Adopt multifunctional water treating agent of the present invention, only need a dosing, only need a kind of medicine machine, and determine, can easily, accurately determine to add dose, avoided the waste of medicament owing to various pharmacodynamic features.
Be the multifunctional water treating agent that exploitation does not have above-mentioned shortcoming, the inventor has carried out intensive research.As a result, the contriver has unexpectedly found technical scheme of the present invention in to the scale inhibition of two ((phosphonomethyl)) aspartic acid, process that rust inhibition is studied.
As everyone knows, every having-P (O) OH2 ,-COOH ,-SO3H ,-compound or the polymkeric substance of OH group can be mainly used in protection against corrosion, good antiscale property as the water conditioner of recirculated cooling water, generally be referred to as inhibiter, Scale inhibitors.Two ((phosphonomethyl)) aspartic acids with phosphono and carboxyl just have good scale inhibition, inhibition dual-use function; even the water of high rigidity also had good scale-inhibiting properties, simultaneously, this compound is the L-aspartame; belong to environmentally friendly machine, can not cause environmental pollution.Composite the forming of multifunctional water treating agent system's employing of the present invention.The inventor finds that unexpectedly inciting somebody to action two ((phosphonomethyl)) aspartic acids (BPMA, surplus same) is basic material; with be selected from 1-hydroxyl-1; 1-two phosphono ethane (HEDP, surplus same), 1-hydroxyl-1-phosphine acyl acetic acid (HPA; surplus same); 2-phosphonic acids butane-1,2,4-three carboxyl (PBTCA; surplus same); poly-phosphono-carboxylic acids (PPCA, surplus same), vinylformic acid/methyl acrylate copolymer (AA/MA; surplus same); vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer (AA/MA/HEA, surplus same), sulfonated phenylethylene/maleic anhydride copolymer (SSMAC; surplus same); one or more materials in the zinc salt etc. are composite, not only do not reduce its scale inhibition; corrosion inhibition makes its scale inhibition on the contrary; corrosion inhibition obviously improves; in addition, can play cleaning simultaneously; the effect of pre-film.
The multifunctional water treating agent that is used for recirculating cooling water system of the present invention comprises following component: a) N of 8～30wt%, two ((phosphonomethyl)) aspartic acids of N-, preferred 14～24wt%, preferred especially 15～20wt%; B) 0.3～30wt%'s is selected from 1-hydroxyl-1,1-two phosphono ethane, 1-hydroxyl-1-phosphine acyl acetic acid, 2-phosphonic acids butane-1,2,4-three carboxyls, poly-phosphono-carboxylic acids, polyacrylic acid, methyl acrylate copolymer, polyacrylic acid, methyl acrylate, Hydroxyethyl acrylate terpolymer, one or more materials of poly-sulfonated phenylethylene, maleic anhydride copolymer, preferred 6～25wt%; C) zinc salt of 0.0001～20wt%, preferred ZnCl
2Preferred 2～the 6wt% of the content of zinc salt, preferred especially 3～5wt%; Surplus is a water.
Below the present invention is carried out more detailed description.Before disclosure and description recirculated cooling water multifunctional water treating agent of the present invention, need point out that the present invention is not limited to the restriction of special construction described herein, method steps and material, these structures, method steps and material can change to some extent.
Though the present invention preferably uses N, two ((phosphonomethyl)) aspartic acids of N-, a lot of having-P (O) OH
2,-COOH ,-SO
3H ,-compound or the polymkeric substance of OH group can be as base stock of the present invention (a).
The content of component (a) can adopt different usage quantitys neatly according to different quality.This depends on the purpose that will reach, and the difference of water quality.When to scale inhibition, when corrosion inhibition is had relatively high expectations, the content of component (a) is just more, otherwise, just lack.
Component (b) can be any compound or the mixture with cleaning, pre-film effect.Preferred those can improve the scale inhibition of component (a) and the material of inhibition synergistic effect.The preferred 1-hydroxyl-1 of the present invention; 1-two phosphono ethane (production of Dongfanghong chemical plant, Tianjin); 1-hydroxyl-1-phosphine acyl acetic acid (the new Da Yu in Beijing product B C-607 of technology company); 2-phosphonic acids butane-1; 2; 4-three carboxyls (production of Wujin, Jiangsu water quality stabilizer factory); poly-phosphono-carboxylic acids (the new Da Yu in Beijing product B C-630 of technology company); vinylformic acid/methyl acrylate copolymer (the new Da Yu in Beijing product B C-645 of technology company); vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer (the new Da Yu in Beijing product B C-646 of technology company), one or more materials in the sulfonated phenylethylene/maleic anhydride copolymer (the new Da Yu in Beijing product B C-647 of technology company) are as component (b).
As the poly-phosphono-carboxylic acids of component (b), vinylformic acid/methyl acrylate copolymer, vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer, the molecular weight of sulfonated phenylethylene/maleic anhydride copolymer is not particularly limited.But the molecular weight of preferred various polymkeric substance is generally: poly-phosphono-carboxylic acids 1000～8000; vinylformic acid/methyl acrylate copolymer 1000～8000; vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer 1000～8000; sulfonated phenylethylene/maleic anhydride copolymer 1000～8000; particularly preferred molecular weight is respectively: poly-phosphono-carboxylic acids 2000～5000; vinylformic acid/methyl acrylate copolymer 2000～5000; vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer 2000～5000, sulfonated phenylethylene/maleic anhydride copolymer 2000～5000.
The content and the combination thereof of various copolymerization units are not particularly limited in the used multipolymer of the present invention.
The example of preferred vinylformic acid/methyl acrylate copolymer has:
General formula of molecular structure:
Monomer is formed: X～95% Y～5%
Solid content: 30%
Polymericular weight: the new Da Yu in 2000～5000 Beijing product B C-645A of technology company
The example of preferred vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer has:
General formula of molecular structure:
Monomer is formed: X～85% Y～5% Z～10%
Solid content: 30%
Polymericular weight: the example of the preferred sulfonated phenylethylene of the new Da Yu in 2000～5000 Beijing product B C-646 of technology company/maleic anhydride copolymer has: general formula of molecular structure:
Monomer is formed: X～55% Y～45% solid content: 50% polymericular weight: the new Da Yu in 2000～5000 Beijing product B C-647 of the technology company preferably example of poly-phosphono-carboxylic acids has: monomer is formed: butene dioic acid～80%; vinylformic acid～10%; inferior sodium phosphate～10% solid content: 35% polymericular weight: the content of the new Da Yu in 2000～4000 Beijing product B C-630 of technology company component (b) can adopt different usage quantitys neatly according to different quality and different purposes equally.When needs clean preferably, pre-film effect, the consumption of component (b) can be greatly, otherwise, can be smaller.
Component (c) can be ZnCl
2Perhaps ZnSO
47H
2O.These can be buied from Beijing Raw Materials Company of Chemical Industry.
The consumption of component (c) also can be grasped by actual needs flexibly.
In sum, essence of the present invention is the combination of each component, has provided in the amount ranges in technical scheme of the present invention, and the user can be according to different water quality and different application target adjustment prescriptions.The adjustment technology of each component content of the present invention is conventional technology to those skilled in the art.When using multifunctional water treating agent of the present invention, also can adopt different usage quantitys neatly.
Compared with prior art, adopt multifunctional water treating agent of the present invention, only need to use a cover medicine machine, only need carry out a dosing, the medicament synergistic effect problem that need consider in the time of need not considering to use a plurality of medicament before the dosing, it is more much smaller when using multiple special agent than comprehensive to add dose, therefore use simple, convenient, can play the effect of cleaning, pre-film, scale inhibition, inhibition, not only function is many, and effective.
The following examples have been done to further describe to technical scheme of the present invention, and these embodiment are for the present invention is described, rather than limitation of the present invention.
In the following embodiments, as not particularly pointing out, the each component consumption is 100 weight parts in BPMA.
In the following embodiments, remove ZnCl
2Outside solid, unless specialize, used various materials are the aqueous solution, and described consumption also is meant the consumption of the corresponding aqueous solution, and the unit of consumption is parts by weight.
The weight concentration of the aqueous solution of various materials is:
Embodiment 1
| The sample title | Sample concentration wt% |
| ????BPMA | ??28～30 |
| ????HPA | ??35～40 |
| ????HEDP | ????50 |
| ????PBTCA | ????50 |
| ????AA/MA | ????30 |
| ???AA/MA/HEA | ????30 |
| ????SSMAC | ????50 |
| ????PPCA | ??30～40 |
| ????ZnCl 2 | Solid |
BPMA????????100
HPA?????????26.67
ZnCl
2??????6.67
Embodiment 2
BPMA????????100
HEDP????????18.75
ZnCl
2??????6.25
Embodiment 3
BPMA???????100
HPA????????13.33
SSMAC??????13.33
ZnCl
26.67 embodiment 4
BPMA?????????100
PBTCA????????18.75
ZnCl
2???????6.25
Embodiment 5
BPMA????????100
HPA?????????14.28
AA/MA/HEA???21.43
ZnCl
2??????7.14
Embodiment 6
BPMA????????100
PPCA????????36.36
SSCAC???????18.18
AA/MA???????18.18
ZnCl
2??????9.09
Embodiment 7
BPMA?????????100
HEDP?????????60
AA/MA/HEA????30
ZnCl
2???????10
Embodiment 8
BPMA????????100
HPA?????????36.36
SCCAC???????18.18
AA/MA/HEA???18.18
ZnCl
2??????9.09
1. scale inhibition performance is measured
In " the water coolant analysis and the test method " of present method according to production department of China PetroChemical Corporation, development division announcement, static-state scale inhibition tosca method is tested.Prepare calcium ion and bicarbonate ion concentration 250mg/L, add the Scale inhibitors of required evaluation, under 80 ℃ ± 1 temperature, evaporation concentration after constant temperature leaves standstill 10 hours, is analyzed calcium ion content in the clear liquor approximately to 2 times, the evaluation scale-inhibiting properties.
Reagent: preparation CaCl2, NaHCO3 reference liquid.
Instrument: 1. porous thermostat water bath
2. meter glass is 1000 milliliters
3. volumetric flask is 500,100 milliliters
4. transfer pipet
5. acidometer calculation result:
Ca
0 2+: the Ca of actual measurement before the test solution test
2 2+Concentration multiply by cycles of concentration and the theoretical Ca that obtains again
2 2+Concentration.
Ca
1 2+: add the test solution of Scale inhibitors, the Ca after the test
2 2+Concentration.
Ca
2 2+: do not add Scale inhibitors test solution (blank), Ca under the same conditions
2 2+Concentration
| The sample title | Sample size/mg/L | Scale inhibition performance/% |
| ??BPMA | ????30 | ????88.70 |
| ??AA/MA | ????30 | ????86.96 |
| Embodiment 1 | ????30 | ????83.40 |
| Embodiment 2 | ????30 | ????87.07 |
| Embodiment 3 | ????30 | ????87.60 |
| Embodiment 4 | ????30 | ????90.91 |
| Embodiment 5 | ????30 | ????89.38 |
| Embodiment 6 | ????30 | ????88.53 |
| Embodiment 7 | ????30 | ????86.99 |
| Embodiment 8 | ????30 | ????80.73 |
2. corrosion inhibition rate is measured
" water coolant analysis and test method " middle laboratory corrosion inhibition rate evaluation that present method is announced according to production department of China PetroChemical Corporation, development division is the performance evaluation that the rotary hanging plate weight-loss method is carried out corrosion inhibition rate, cleaning, pre-film.
Instrument: RCC-1 type rotary hanging plate corrosion test instrument
2000 milliliters in beaker
Condition: test material: 20# carbon steel
Test temperature: 50 ± 1 ℃
Time: 72 hours
Rotating speed: 70 rev/mins
Calculation result:
C: computational constant, when being unit with mm/a, C=8.76 * 10
7Δ ω: the corrosion weight loss of test piece (gram) A: test piece area (cm
2) T: the test piece test period (hour) P: the density (kilogram/rice of test piece material
3)
3. clean (the same corrosion inhibition rate of testing method) dosing 1000～3000mg/L, decide according to corrosion in the system, fouling situation, scavenging period 36～48 hours can clean up substantially.
4. pre-film (testing method and corrosion inhibition rate are basic identical)
| The sample title | Sample size/mg/L | Tap water corrosion speed/mm/a | Softening water corrosion speed/mm/a |
| ????BPMA | ????30 | ????0.0613 | ????0.0705 |
| ????HEDP | ????30 | ????0.0070 | ????0.0360 |
| Embodiment 1 | ????30 | ????0.0513 | ????0.0645 |
| Embodiment 2 | ????30 | ????0.0576 | ????0.0624 |
| Embodiment 3 | ????30 | ????0.0135 | ????0.0415 |
| Embodiment 4 | ????30 | ????0.0437 | ????0.0598 |
| Embodiment 5 | ????30 | ????0.0365 | ????0.0632 |
| Embodiment 6 | ????30 | ????0.0090 | ????0.0162 |
| Embodiment 7 | ????30 | ????0.0066 | ????0.0113 |
| Embodiment 8 | ????30 | ????0.0099 | ????0.0167 |
| The sample title | Sample size/mg/L | 20# corrosion of carbon steel rate/mm/a | Full rust 20# corrosion of carbon steel rate/mm/a | Cleaning performance |
| Embodiment 6 | ??1000 | ??0.0017 | ||
| ??2000 | ??0.0955 | ????0.3334 | The greyish black surface of spending | |
| Embodiment 7 | ??1000 | ??0.0074 | ||
| ??2000 | ??0.0894 | ????0.3360 | The greyish black surface of spending | |
| Embodiment 8 | ??1000 | ??0.0054 | ||
| ??2000 | ??0.0642 | ????0.3313 | The greyish black surface of spending |
Dosing 400～700mg/L, material 20# carbon steel, room temperature rotary hanging plate method, 48 hours time.
Lacing film is through electronic microscope photos, and the film of formation is to the infiltration of metal nexine, and thickness reaches 70 μ m, and concrete outcome is as follows:
| Sample | Sample size/mg/L | Corrosion rate/mm/a | Surface phenomena | Thickness/μ m |
| Embodiment 6 | ????500 | ????0.0023 | Shallow blue band is yellow | ????40 |
| Embodiment 7 | ????500 | ????0.0021 | Avy blue | ????65 |
| Embodiment 8 | ????500 | ????0.0031 | Avy blue | ????70 |
Above-mentioned scale inhibitor cleans pre-film experiment and shows, the maximum characteristics of multifunctional water treating agent of the present invention are to use simply, convenience, and not only function is many, and effective.
Claims (7)
1, a kind of multifunctional water treating agent that is used for recirculating cooling water system comprises following component:
A) N of 8～30wt%, the two (phosphonomethyl) aspartic acids of N-;
B) 0.3～30wt%'s is selected from 1-hydroxyl-1,1-two phosphono ethane, 1-hydroxyl-1-phosphine acyl acetic acid, 2-phosphonic acids butane-1,2,4-three carboxyls, poly-phosphono-carboxylic acids, vinylformic acid/methyl acrylate copolymer, vinylformic acid/methyl acrylate/Hydroxyethyl acrylate terpolymer, one or more materials in sulfonated phenylethylene/maleic anhydride copolymer;
C) zinc salt of 0.0001～20wt%;
Surplus is a water.
2, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 1 is characterized in that: described component content a) is 14～24wt%.
3, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 2 is characterized in that: described component content a) is 15～20wt%.
4, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 1 is characterized in that: content described component b) is 6～25wt%.
5, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 1 is characterized in that: content described component c) is 2～6wt%.
6, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 5 is characterized in that: content described component c) is 3～5wt%.
7, the multifunctional water treating agent that is used for recirculating cooling water system according to claim 1 is characterized in that: described zinc salt is ZnCl
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001249983A CN1145585C (en) | 2000-09-29 | 2000-09-29 | Multi-function water treatment agent for circulating water cooling system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001249983A CN1145585C (en) | 2000-09-29 | 2000-09-29 | Multi-function water treatment agent for circulating water cooling system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1345696A true CN1345696A (en) | 2002-04-24 |
| CN1145585C CN1145585C (en) | 2004-04-14 |
Family
ID=4590801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001249983A Expired - Fee Related CN1145585C (en) | 2000-09-29 | 2000-09-29 | Multi-function water treatment agent for circulating water cooling system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1145585C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427413C (en) * | 2005-05-25 | 2008-10-22 | 北京化工大学 | Trielement synergistic corrosion inhibitor |
| CN101368091B (en) * | 2007-08-16 | 2012-01-11 | 中国石油天然气集团公司 | Oil well cement retarder |
| CN102583785A (en) * | 2012-02-03 | 2012-07-18 | 上海韬鸿化工科技有限公司 | Circulating cooling water corrosion inhibitor, and preparation and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665684B (en) * | 2009-09-28 | 2012-07-04 | 大庆油田有限责任公司 | Anti-scaling agent for oil well silicate scale |
-
2000
- 2000-09-29 CN CNB001249983A patent/CN1145585C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427413C (en) * | 2005-05-25 | 2008-10-22 | 北京化工大学 | Trielement synergistic corrosion inhibitor |
| CN101368091B (en) * | 2007-08-16 | 2012-01-11 | 中国石油天然气集团公司 | Oil well cement retarder |
| CN102583785A (en) * | 2012-02-03 | 2012-07-18 | 上海韬鸿化工科技有限公司 | Circulating cooling water corrosion inhibitor, and preparation and application thereof |
| CN102583785B (en) * | 2012-02-03 | 2013-05-08 | 上海韬鸿化工科技有限公司 | Circulating cooling water corrosion inhibitor, and preparation and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1145585C (en) | 2004-04-14 |
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