CN1869288A - Method for preparing anti-corrosion film on metal surface - Google Patents
Method for preparing anti-corrosion film on metal surface Download PDFInfo
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- CN1869288A CN1869288A CN 200510072251 CN200510072251A CN1869288A CN 1869288 A CN1869288 A CN 1869288A CN 200510072251 CN200510072251 CN 200510072251 CN 200510072251 A CN200510072251 A CN 200510072251A CN 1869288 A CN1869288 A CN 1869288A
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Abstract
The invention relates to a manufacture method for metal surface corrosion protection film that forms mixed equal pre-film liquid from PESA or PESA salt, zinc salt and phosphate, xanthate or polyocarboxy acid, under 20-60 degree centigrade, using the pre-film liquid contact to the metal surface for 24-27h, the film would be formed. The invention has little medicament dosage, and short filming time. It has wonderful anti corruption ability. It has simple filming process and decreases the discharge of waste liquid.
Description
Technical field
The present invention relates to a kind of method for preparing anti-corrosion film in the metallic surface, can be used for the corrosionproof protection of Treatment of Industrial Water, particularly treatment of cooling water and Waste Water Treatment metallic surface.
Background technology
The unify preparation (pre-film) of waste water system anti-corrosion film on metal surface of existing cooling water system is to do pre-film liquid with Sodium hexametaphosphate 99 and zinc sulfate, phosphorus content height, consumption greatly (400 ~ 800mg/L), environment is polluted.
Poly-epoxy succinic acid (PESA) is a kind of water-soluble polymers with powerful chelating and scale inhibition performance, and not phosphorous and nitrogen element can not cause body eutrophication in its molecular structure, and biodegradable is good, is a kind of green polymer.Water treatment method based on PESA is the forward position of present water technology.Scale inhibitors or antiseptic corrosion inhibitor when publication is generally all moved as water system with the PESA prescription, as: United States Patent (USP) " Method of inhibiting corrosion in aqueous systems " [US5,256,332 (1993)] provide a kind of prescription of being made up of phosphoric acid salt, azole compounds, PESA and acrylic copolymer, the anti-corrosion, scale-inhibiting that is used for the recirculating cooling water system run duration is handled.U.S. Pat 5,342,540 (1994) " Compositions for controlling scale formation in aqueous system " provide Xiang Shuizhong to add the method for scale inhibition of PESA, acrylic copolymer and lanthanide ion, and lanthanide ion has stoped the interaction of PESA and acrylic copolymer effectively.United States Patent (USP) " US P6; 645; 400 have proposed the technology that a kind of metallic surface at water system prepares anti-corrosion film; be that main component is done pre-film liquid with the hydrogen peroxide; wherein can add tens kinds of acid such as PESA; form passive film in the metallic surface, this technology film formation time grow (about a week), and consumption also (200mg/L) greatly; Implementation process is comparatively complicated, needs to regulate pH, needs substitutional solution etc. before the operation.At present be that the preservative protective film that water treatment and Waste Water Treatment metallic surface are done in the basis yet there are no report with PESA.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of metallic surface corrosion prevention film based on PESA.This method is pollution-free, and the prefilming agent consumption is few, and implementation method is simple.
The preparation method of anti-corrosion film on metal surface of the present invention is, be mixed into pre-film liquid with A, B and three kinds of components of C, wherein the A component is: poly-epoxy succinic acid (PESA) or polyepoxysuccinic acid salt (PESA salt), the B component is a zinc salt, the C component is phosphoric acid salt, xanthogenate or polycarboxylate, the A component concentration is that benchmark is counted 30～50mg/L with the PESA disodium in the pre-film liquid, and B component zinc salt consumption is with Zn
2+For benchmark is counted 2～4mg/L, the C amounts of components is that benchmark is counted 20～50mg/L with polyvalent alcohol phosphonic acid ester (PAPE), under 20～60 ℃, contacts 24～72h with pre-film liquid with the metallic surface, can generate the film with corrosion proof function in the metallic surface.
The salt of above-mentioned PESA can be an alkali metal salt or the alkaline earth salt of PESA.
Above-mentioned zinc salt mainly utilizes zine ion to react, and generally can be for example zinc sulfate, zinc chloride or zinc nitrates etc. of various zinc salts.
Above-mentioned phosphoric acid salt and PESA work in coordination with film forming, can be Sodium hexametaphosphate 99, polyvalent alcohol phosphonic acid ester (PAPE) or phosphine carboxylic acid etc.
Above-mentioned xanthogenate is a sodium xanthonate; Polycarboxylate is hydrolytic polymaleic anhydride (HPMA) or copolymer-maleic anhydride; They mainly play stable zinc ion action.
Dosing of the present invention little (104mg/L), film formation time is short, (be 24 ~ 72h), prepared metallic surface precipitation membrane Corrosion Protection is good, check with standard copper sulfate topical application, the solidity to corrosion of the metal surface film that the present invention is prepared reaches 170s, be much better than recirculating cooling water system do not stop matting and hot pre-membrane process technical regulation (CECS103:99) defined technical indicator (＞10s).Film forming implementation process of the present invention is simple, and pre-film liquid need not replace and discharge and can put into operation, has therefore reduced the discharging of waste water.
Embodiment
Embodiment 1: add PESA sodium salt 50mg/L (in the PESA disodium salt) in standard corrosive water (containing Calcium dichloride dihydrate 735mg/L, sal epsom 493mg/L, sodium-chlor 658mg/L and sodium bicarbonate 168mg/L), zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrodes contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 166s.
Embodiment 2: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 24h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 100s.
Embodiment 3: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 20 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 125s.
Embodiment 4: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 60 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 170s.
Embodiment 5: add PESA calcium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 165s.
Embodiment 6: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc sulfate 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 166s.
Embodiment 7: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc nitrate 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 166s.
Embodiment 8: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), Sodium hexametaphosphate 99 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 165s.
Embodiment 9: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), phosphine carboxylic acid 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 166s.
Embodiment 10: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), sodium xanthonate 50mg/L (in sodium xanthonate) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 166s.
Embodiment 11: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), HPMA 50mg/L (in HPMA) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 164s.
Embodiment 12: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), copolymer of maleic anhydride and acrylic acid 50mg/L (in HPMA) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 164s.
Embodiment 13: add PESA sodium salt 30mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 108s.
Embodiment 14: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 2mg/L is (with Zn
2+Meter), PAPE 50mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 58s.
Embodiment 15: add PESA sodium salt 50mg/L (in the PESA disodium salt) in the standard corrosive water, zinc chloride 4mg/L is (with Zn
2+Meter), PAPE 20mg/L (in PAPE) mixes, and makes pre-film liquid.Under 40 ℃ of temperature, make pre-film liquid with standard 20 steel electrode test pieces contact 72h, promptly generate film with corrosion proof function in the metallic surface.With the check of standard copper sulfate topical application, the solidity to corrosion of prepared metal surface film is 85s.
Claims (6)
1, a kind of preparation method of anti-corrosion film on metal surface, comprise configuration pre-film liquid and in the metallic surface film forming, it is characterized in that, be mixed into pre-film liquid with A, B and three kinds of components of C, wherein the A component is: poly-epoxy succinic acid or polyepoxysuccinic acid salt, and the B component is a zinc salt, the C component is phosphoric acid salt, xanthogenate or polycarboxylate, the A amounts of components is that benchmark is counted 30～50mg/L with the poly-epoxy succinic acid disodium in the pre-film liquid, and B component zinc salt consumption is with Zn
2+For benchmark is counted 2～4mg/L, the C amounts of components is that benchmark is counted 20～50mg/L with the polyvalent alcohol phosphonic acid ester, under 20～60 ℃, contacts 24～72h with pre-film liquid with the metallic surface, at anti-corrosion film on metal surface.
2, method according to claim 1 is characterized in that, polyepoxysuccinic acid salt is an alkali metal salt or the alkaline earth salt of poly-epoxy succinic acid.
3, method according to claim 1 is characterized in that, zinc salt is zinc sulfate, zinc chloride or zinc nitrate.
4, method according to claim 1 is characterized in that, phosphoric acid salt, is Sodium hexametaphosphate 99, polyvalent alcohol phosphonic acid ester or phosphine carboxylic acid.
5, method according to claim 1 is characterized in that, xanthogenate is a sodium xanthonate.
6, method according to claim 1 is characterized in that, polycarboxylate is hydrolytic polymaleic anhydride or copolymer-maleic anhydride.
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| CNB2005100722511A CN100398698C (en) | 2005-05-27 | 2005-05-27 | Method for preparing anti-corrosion film on metal surface |
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| CNB2005100722511A CN100398698C (en) | 2005-05-27 | 2005-05-27 | Method for preparing anti-corrosion film on metal surface |
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| CN100398698C CN100398698C (en) | 2008-07-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080233A (en) * | 2010-12-23 | 2011-06-01 | 常州市科威精细化工有限公司 | Phosphorus-free prefilming agent for prefilming treatment of circulating cooling water system and application method thereof |
| CN102703906A (en) * | 2012-05-30 | 2012-10-03 | 嘉应学院 | Corrosion inhibitor for inhibiting titanium from being corroded in acid liquor |
| CN103130340A (en) * | 2011-11-30 | 2013-06-05 | 安徽省蓝天化工有限公司 | Preparation method of scale and corrosion inhibitors for electrical power system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438185A (en) * | 2003-01-25 | 2003-08-27 | 王海宁 | Green scale and corrosion inhibitor |
| CN1255338C (en) * | 2003-10-20 | 2006-05-10 | 北京化工大学 | Water treating method with scale and corrosion inhibitor containing epoxy amber acid polymer |
| CN1321077C (en) * | 2003-11-12 | 2007-06-13 | 中国石油化工股份有限公司北京燕山分公司研究院 | Composite scale-proof corrosion inbibitor containing poly epoxy succinic acid and its use |
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2005
- 2005-05-27 CN CNB2005100722511A patent/CN100398698C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080233A (en) * | 2010-12-23 | 2011-06-01 | 常州市科威精细化工有限公司 | Phosphorus-free prefilming agent for prefilming treatment of circulating cooling water system and application method thereof |
| CN102080233B (en) * | 2010-12-23 | 2012-05-30 | 常州市科威精细化工有限公司 | Phosphorus-free prefilming agent for prefilming treatment of circulating cooling water system and application method thereof |
| CN103130340A (en) * | 2011-11-30 | 2013-06-05 | 安徽省蓝天化工有限公司 | Preparation method of scale and corrosion inhibitors for electrical power system |
| CN102703906A (en) * | 2012-05-30 | 2012-10-03 | 嘉应学院 | Corrosion inhibitor for inhibiting titanium from being corroded in acid liquor |
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