CN1119297C - Composite anticorrosion antifoulant for softening circulated water - Google Patents
Composite anticorrosion antifoulant for softening circulated water Download PDFInfo
- Publication number
- CN1119297C CN1119297C CN99122124A CN99122124A CN1119297C CN 1119297 C CN1119297 C CN 1119297C CN 99122124 A CN99122124 A CN 99122124A CN 99122124 A CN99122124 A CN 99122124A CN 1119297 C CN1119297 C CN 1119297C
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- Prior art keywords
- acid
- salt
- recombiner
- water
- zinc
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Abstract
The present invention provides a compounded corrosion and scale inhibitor which comprises the components (measured by adopting the weight of the composition as 100%) of 5 to 35% of carboxyl sulfonic acid copolymers, 5 to 35% of phosphate, 2 to 10% of zinc salts and water. Furthermore, the compounded agent can also contain azole compounds, organic phosphonic acid or the salts thereof and organic phosphino carboxylic acid or the salts thereof. The compounded agent of the present invention which does not contain nitrites and chromates or molybdenates has the advantages of low cost, non-poisonousness, no environmental pollution and good treatment effect. In addition, the present invention is applicable to circulating water with the softened water quality of 0 to 15 mg/L of calcium hardness, and the common concentration for use is 15 to 150 mg/L.
Description
The invention belongs to the composition of the inhibition metallic corrosion of using in the water treatment, a kind of composite slow-corrosion scale resistor that is used for demineralized water recirculated water of more specifically saying so.
In the Treatment of Industrial Water field, there are quite a few full scale plant reasons such as temperature height special owing to the position that is cooled or medium need use softening water to make recirculated cooling water, the recirculated cooling water that is used to cool off the oxygen rifle as metallurgical system, the recirculated cooling water of nuclear power generating system, the water coolant that float glass need be used and the recirculated cooling water of central air conditioner system etc.The softening recirculated water calcium that is used for such use is generally 0mg/L～15mg/L firmly (with Ca
2+Meter, down together), most about 4mg/L.The distinguishing feature of this class water quality is a non-scaling, and is extremely strong to corrosion of metal, and therefore, to the processing of this class water quality, key is the etching problem that solves hardware.Up to the present, the nitrite or the chromic salt of high density are usually adopted in the processing of this class water quality, and this method treatment effect is good, and the erosion rate of carbon steel metalloid can be less than 0.025mm/, but nitrite and chromic salt are the intensive carcinogenic substances, and environmental pollution is serious.
The eighties occurs a kind of phosphorous low, and corrosion mitigating effect is organic phosphine carboxylic acid corrosion inhibiting and descaling agent 2-hydroxyl phosphino-acetate (HPAA) preferably, makes the state of the art of handling soft water quality that new raising arranged.For example US4717542 employing HPAA/ polymkeric substance is the prescription of main component, is used to handle calcium and is the recirculated water about 80mg/L firmly.CN1176229A adopts composite compound prescriptions such as HPAA and organic phosphine carboxylic acid, can handle calcium and be the water quality about 20mg/L firmly, treatment effect is better, the erosion rate of carbon steel metalloid can be less than 0.05mm/, but bad to the water treatment effect below the hard 10mg/L of calcium, particularly can not be used to handle the calcium water quality below 5mg/L firmly.
These class water of Combined Processing such as the nineties patent RO111789 report employing molybdate and sodium lignosulfonate, nitrite.The treatment effect of this recombiner is better, compares with the method for simple employing nitrite, and the consumption of nitrite reduces significantly, but still needs to use a certain amount of nitrite, and problem of environment pollution caused still exists, and secondly is the processing costs height; The JP04330998 report adopts inorganic orthophosphate or inorganic polyphosphate, the lipid acid of 20～300mg/L and the organic polyethylene polyamine Combined Processing softened water for boiler of 10～20mg/L of 5～60mg/L, this recombiner can prevent the corrosion and the fouling of boiler preferably, but the treatment agent using dosage is big, and cost is higher.
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of nitrite, chromic salt or molybdate of not containing is provided, nontoxic, cost is low, and is free from environmental pollution, and treatment effect is good, is applicable to the composite slow-corrosion scale resistor of demineralized water recirculated water.
Composite slow-corrosion scale resistor provided by the invention (calling recombiner in the following text) comprising: in composition weight is 100%, carboxylic sulfonic acid copolymer 5～35%, phosphoric acid ester 5～35%, zinc salt 2～10% (in zinc), and water.
Described carboxylic sulfonic acid copolymer is a kind of novel dirt dispersion agent, can be selected from the copolymer of vinylformic acid and 2-acrylamide-2-methyl-propanesulfonic acid (AMPS), vinylformic acid and AMPS, the terpolymer of maleic anhydride, vinylformic acid and AMPS, maleic anhydride, the tetrapolymer of phospho acid, the copolymer of vinylformic acid and allyl group hydroxypropyl sulfonic acid, vinylformic acid and allyl group hydroxypropyl sulfonic acid, one of terpolymer of acrylate or its mixture, the copolymer of preferred vinylformic acid and AMPS, vinylformic acid and AMPS, the copolymer of the terpolymer of maleic anhydride or vinylformic acid and allyl group hydroxypropyl sulfonic acid, the more preferably copolymer of vinylformic acid and AMPS.The content of carboxylic sulfonic acid copolymer in recombiner is 5～35%, and is preferred 10～30%, more preferably 15～30%.
Described phosphoric acid ester is a kind of good inhibiter, can be PAPE or Aethoxy Sklerol amine phosphoric acid ester.Wherein PAPE comprises ternary, quaternary, hexavalent alcohol phosphoric acid ester, as glycerol phosphoric acid ester, pentaerythritol phosphate, and hexan-hexol phosphoric acid ester or the like, preferred hexavalent alcohol phosphoric acid ester.The content of phosphoric acid ester in recombiner is 5～35%, and is preferred 10～30%, more preferably 15～30%.
Described zinc salt is a soluble zinc salt, as zinc chloride, zinc sulfate or zinc nitrate etc.Zinc salt is the inorganic inhibitor of using always, generally need and dirt dispersion agent and the compound use of other inhibiter, and content is 2～10% (in zinc) in recombiner preferred 3～7%.
Can also contain azole compounds in the recombiner provided by the invention, as benzotriazole (BZT), mercaptobenzothiazole (MBT) etc., this compounds has good corrosion mitigating effect to copper equipment.The content of azole compounds in recombiner is 0～2%, is preferably 0.2～0.8%.
Recombiner provided by the invention can also contain organic phospho acid or its salt, with its corrosion inhibition of further raising.Organic phospho acid or its salt can be 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP) and their sylvite (HEDPK
n, ATMPK
n, EDTMPK
n), sodium salt (HEDPNa
n, ATMPNa
n, EDTMPNa
n), n can be 1,2,3 or 4 in the formula, preferred 2,4; Organic phospho acid or the content of its salt in recombiner are 0～20%, preferred 2～16%.
Recombiner provided by the invention can also contain organic phosphine carboxylic acid or its salt, with its anticorrosion-antiscaling property of further raising.Organic phosphine carboxylic acid or its salt can be hydroxyl phosphino-acetate (HPAA) and phosphono-containing butane-1,2,4-tricarboxylic acid (PBTC) and their sylvite (HPAK
n, PBTCK
n), sodium salt (HPAKNa
n, PBTCNa
n) or ammonium salt, n can be 1,2,3 or 4 in the formula, preferred 2,4.Organic phosphine carboxylic acid or the content of its salt in recombiner are 0～20%, preferred 2～16%.
Recombiner component carboxylic sulfonic acid copolymer provided by the invention, phosphoric acid ester, zinc salt, azole compounds, organic phosphonate and organic phosphine carboxylic acid all are the commercially available prod, and except that zinc salt and azole compounds are the solid, other all is an aqueous products.Only need when composite each component is with in the acid-resistant container that stirs by joining for certainty ratio successively, stirring promptly obtains desired product.
Recombiner of the present invention is applicable to that calcium is the softening circulating water treatment of 0～15mg/L firmly, circulating water system can be handled through pre-film during use, also can handle without pre-film, the recombiner for preparing is directly joined circulating water system according to given concentration, working concentration is generally 15～150mg/L (to do agent, be preferably 25～45mg/L down together).
Recombiner provided by the invention has the following advantages: do not contain deleterious materials such as nitrite and chromic salt in (1) recombiner, and safe in utilization, free from environmental pollution.(2) do not contain inorganic poly-phosphorus and amine substance in the recombiner, help microbiological manipulation in the recirculated water, alleviate when discharging yet the environment eutrophication pollution.(3) do not contain expensive materials such as molybdate in the recombiner, make the cheap of recombiner.(4) recombiner adopts inhibiter such as PAPE and zinc salt, and treatment effect is good, and the erosion rate of carbon steel metalloid can reach the treatment effect of nitrites inhibiter less than 0.025mm/.(5) contain new and effective dirt dispersion agents such as carboxylic sulfonic acid copolymer in the recombiner of the present invention, inorganic salt in the recirculated water and corrosion product are deposited good inhibition effect on the high temperature heat transfer face, scale inhibition performance can reach 100%.(6) recombiner working concentration of the present invention reduces about than the 1000mg/L of nitrite significantly, only needs to use 25～45mg/L, and the salts contg in the softening recirculated water is reduced significantly.
Further specify characteristics of the present invention below by embodiment.
Example 1
This example is with 20
#Carbon steel is rotated coupon corrosion test.
The preparation of recombiner: with the carboxylic sulfonic acid copolymer (RP-35, the water stabilizer production of Beijing woods China) of 20 parts of vinylformic acid and AMPS, 20 parts of hexan-hexol PAPE (PC-604, the water stabilizer production of Beijing woods China), 19.5 parts of ZnSO
47H
2O (in 4.4 parts on zinc), 5 parts of HEDP, 5 parts of PBTC, 0.5 part of BZT and 30 parts of deionized waters join respectively in the beaker of 200mL, stir and promptly obtain required recombiner.
The preparation of test water quality: get a certain amount of softening water that obtains through resin cation exchange, adding a certain amount of recombiner, to make the recombiner concentration in the test water be 30mg/L, add a certain amount of yellow soda ash, the pH value of test water is adjusted to 7.0～8.0, obtain test water like this, contain recombiner 30mg/L in the water, the hard 0.2mg/L of calcium, HCO
3 -20mg/L, pH value 7.6.
With reference to the HG/T2195-91 standard, be rotated coupon corrosion test with above-mentioned test water matter, the test water temperature control is at 50 ± 1 ℃, and lacing film rotating speed 75rpm moves 96h continuously, and the test piece erosion rate is 0.0230mm/.
Example 2
This example is with 20
#Carbon steel is rotated coupon corrosion test.
The preparation of recombiner: with the carboxylic sulfonic acid copolymer (RP-35, the water stabilizer production of Beijing woods China) of 28 parts of vinylformic acid and AMPS, 15 parts of hexan-hexol PAPE (PC-604, the water stabilizer production of Beijing woods China), 18 parts of ZnSO
47H
2O (in 4.1 parts on zinc), 4 parts of HPAA, 4 parts of PBTC, 0.5 part of BZT and 30.5 parts of deionized waters join respectively in the beaker of 200mL, stir and promptly obtain required recombiner.
Test water quality is according to example 1 preparation.
According to the method for example 1, be rotated coupon corrosion test with above-mentioned test water matter, the test piece erosion rate is 0.0188mm/.
Example 3
This example is with 20
#Carbon steel is rotated coupon corrosion test.
The preparation of recombiner: with the terpolymer (RP-21, the water stabilizer production of Beijing woods China) of 20 parts of vinylformic acid and allyl group hydroxypropyl sulfonic acid, acrylate, 20 parts of hexan-hexol PAPE (PC-604, the water stabilizer production of Beijing woods China), 18 parts of ZnSO
47H
2O (in 4.1 parts on zinc), 8 parts of HPAA, 8 parts of PBTC, 0.5 part of BZT and 25.5 parts of deionized waters join respectively in the beaker of 200mL, stir and promptly obtain required recombiner.
Test water quality is according to example 1 preparation.
According to the method for example 1, be rotated coupon corrosion test with above-mentioned test water matter, the test piece erosion rate is 0.0128mm/.
Example 4
This example is with 20
#Carbon steel is rotated coupon corrosion test.
The preparation of recombiner: with the carboxylic sulfonic acid copolymer (RP-35, the water stabilizer production of Beijing woods China) of 20 parts of vinylformic acid and AMPS, 20 parts of hexan-hexol PAPE (PC-604, the water stabilizer production of Beijing woods China), 18 parts of ZnSO
47H
2O (in 4.1 parts on zinc), 42 parts of deionized waters join respectively in the beaker of 200mL, stir and promptly obtain required recombiner.
Test water quality is according to example 1 preparation.
According to the method for example 1, be rotated coupon corrosion test with above-mentioned test water matter, the test piece erosion rate is 0.0437mm/.
Example 5
This example is with 20
#Carbon steel is rotated coupon corrosion test.
The preparation of recombiner: with the carboxylic sulfonic acid copolymer (RP-35, the water stabilizer production of Beijing woods China) of 20 parts of vinylformic acid and AMPS, 30 parts of hexan-hexol PAPE (PC-604, the water stabilizer production of Beijing woods China), 18 parts of ZnSO
47H
2O (in 4.1 parts on zinc), 8 parts of HPAA, 8 parts of PBTC, 0.5 part of BZT and 15.5 parts of deionized waters join respectively in the beaker of 200mL, stir and promptly obtain required recombiner.
Test water quality is according to example 1 preparation.
According to the method for example 1, be rotated coupon corrosion test with above-mentioned test water matter, the test piece erosion rate is 0.0103mm/.
Example 6
This example is with 20
#Carbon steel is rotated coupon corrosion test.
According to example 1 preparation recombiner.
The preparation of test water quality: get a certain amount of softening water that obtains through resin cation exchange, adding a certain amount of recombiner, to make the recombiner concentration in the test water be 30mg/L, add a certain amount of yellow soda ash, the pH value of water is adjusted to 7.0～8.0, add a certain amount of calcium chloride again.Obtain test water like this, contain recombiner 30mg/L in the water, the hard 5.0mg/L of calcium, HCO
3 -20mg/L, pH value 7.6.
According to the method for example 1, be rotated coupon corrosion test with above-mentioned test water matter, the test piece erosion rate is 0.0178mm/.
Example 7
This example is with 20
#Carbon steel is rotated coupon corrosion test.
According to example 1, except that the calcium in the test water is increased to the 15mg/L firmly, other test conditions is identical, and the test piece erosion rate is 0.0137mm/.
Example 8
This example adopts red copper to be rotated coupon corrosion test.
Recombiner preparation and test water plasmogamy system are carried out according to example 1.With reference to the HG/T2195-91 standard, be rotated coupon corrosion test with above-mentioned test water matter, the test water temperature control is at 501 ℃, and rotating speed 75rpm moves 96h continuously, and red copper test piece erosion rate is 0.0041mm/.
Example 9
This example is a dynamic analog test.
According to example 1 test preparation recombiner.
Test is made make up water with reference to HG/T2160-91 standard " water coolant dynamic simulation experiment method " with softening water, and the hard 2mg/L that replenishes the calcium mends HCO
3 -15mg/L, the pH value is controlled at 7.0～8.0, and recombiner concentration is controlled at 25～35mg/L.20 of 2 φ 10 * 1 * 530mm
#The carbon steel test tube carries out parallel test, and test water is walked tube side.The heating of test tube external application saturated vapor, 30 ± 1 ℃ of control test water inflow temperatures, 10 ℃ of exit port water temperature difference, the recirculated water cycles of concentration is controlled at 3 ± 0.5, and 400h is carried out in test continuously.The erosion rate that obtains developmental tube is 0.0313mm/, adheres to speed 5.66mg/ (cm
2.mon.).
Example 10
This example is a field application test.
According to example 1 test preparation recombiner.
Field application test is at a cover quantity of circulating water 2500m
3/ h possesses water yield 2000m
3, give 8 ℃ of backwater temperature differences, add the part service water with softening water and make the system of make up water and carry out.Calcium is controlled at 5～15mg/L firmly in the recirculated water, and the pH value is controlled at 7.0～8.0, and drug concentration is controlled at 25～35mg/L.Through 180 days continuous operation, the pre-film test piece average corrosion rate of field monitoring was 0.0103mm/, and not pre-film test piece average corrosion rate is 0.0121mm/, and the iron concentration that forms because of corrosion in the recirculated water is less than 1.0mg/L.
In same circulating water system, use same water quality, adopt to add 1000mg/L nitrite treatments method, the average corrosion rate of field monitoring test piece is 0.0092mm/a, the iron concentration that forms because of corrosion in the recirculated water is less than 1.0mg/L; Adopt to add other organic phosphine, zinc and the processing of organic amine prescription, the calcium in the recirculated water need be added firmly to 15～25mg/L, the pH value is controlled at 7.0～8.0, and drug concentration is controlled at 65～85mg/L.The average corrosion rate of field monitoring test piece is 0.120mm/, and the iron concentration that forms because of corrosion in the recirculated water is up to 10mg/L.
Claims (10)
1. composite slow-corrosion scale resistor that is used for demineralized water recirculated water, comprise: in composition weight is 100%, carboxylic sulfonic acid copolymer 5～35%, phosphoric acid ester 5～35%, in the zinc salt 2～10% of zinc, azole compounds 0～2%, organic phospho acid or its salt are 0～20%, organic phosphine carboxylic acid or its salt 0～20%, and water 15.5～42%.
2. according to the described composite slow-corrosion scale resistor of claim 1, wherein the content of carboxylic sulfonic acid copolymer in recombiner is 10～30%.
3. according to the described composite slow-corrosion scale resistor of claim 1, wherein the content of phosphoric acid ester in recombiner is 10～30%.
4. according to the described composite slow-corrosion scale resistor of claim 1, wherein the content of zinc salt in recombiner counts 3～7% with zinc.
5. according to claim 1 or 2 described composite slow-corrosion scale resistors, wherein the carboxylic sulfonic acid copolymer is selected from the copolymer of vinylformic acid and 2-acrylamide-2-methyl-propanesulfonic acid (AMPS), the terpolymer of vinylformic acid and AMPS, maleic anhydride, the copolymer of the tetrapolymer of vinylformic acid and AMPS, maleic anhydride, phospho acid, vinylformic acid and allyl group hydroxypropyl sulfonic acid, one of terpolymer of vinylformic acid and allyl group hydroxypropyl sulfonic acid, acrylate or its mixture.
6. according to claim 1 or 3 described composite slow-corrosion scale resistors, wherein said phosphoric acid ester is selected from PAPE and Aethoxy Sklerol amine phosphoric acid ester.
7. according to claim 1 or 4 described composite slow-corrosion scale resistors, wherein said zinc salt is selected from zinc chloride, zinc sulfate and zinc nitrate.
8. according to the described composite slow-corrosion scale resistor of claim 1, it is characterized in that azole compounds is selected from benzotriazole, mercaptobenzothiazole or its mixture, the content of azole compounds in recombiner is 0.2～0.8%.
9. according to the described composite slow-corrosion scale resistor of claim 1, it is characterized in that, organic phospho acid or its salt are selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, ethylene diamine tetra methylene phosphonic acid or its mixture and their sylvite and sodium salt, and organic phospho acid or the content of its salt in recombiner are 2～16%.
10. according to the described composite slow-corrosion scale resistor of claim 1, it is characterized in that, organic phosphine carboxylic acid or its salt are selected from hydroxyl phosphino-acetate, phosphono-containing butane-1,2,4-tricarboxylic acid or its mixture and their sylvite, sodium salt and ammonium salt, organic phosphine carboxylic acid or the content of its salt in recombiner are 2～16%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122124A CN1119297C (en) | 1999-10-27 | 1999-10-27 | Composite anticorrosion antifoulant for softening circulated water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122124A CN1119297C (en) | 1999-10-27 | 1999-10-27 | Composite anticorrosion antifoulant for softening circulated water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1294092A CN1294092A (en) | 2001-05-09 |
| CN1119297C true CN1119297C (en) | 2003-08-27 |
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ID=5282315
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99122124A Expired - Lifetime CN1119297C (en) | 1999-10-27 | 1999-10-27 | Composite anticorrosion antifoulant for softening circulated water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101105118B (en) * | 2006-07-11 | 2010-06-30 | 成都孚吉科技有限责任公司 | Solid anti-scaling agent and preparation process thereof |
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| CN101244872B (en) * | 2007-02-16 | 2010-05-19 | 宝山钢铁股份有限公司 | Low-zincium organophosphor scale inhibitor for recirculated cooling water process |
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| CN108715484A (en) * | 2018-05-29 | 2018-10-30 | 苏州佑君环境科技有限公司 | A kind of heat transmission equipment antisludging agent and preparation method thereof |
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-
1999
- 1999-10-27 CN CN99122124A patent/CN1119297C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101105118B (en) * | 2006-07-11 | 2010-06-30 | 成都孚吉科技有限责任公司 | Solid anti-scaling agent and preparation process thereof |
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| Publication number | Publication date |
|---|---|
| CN1294092A (en) | 2001-05-09 |
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