CN100427413C - Trielement synergistic corrosion inhibitor - Google Patents
Trielement synergistic corrosion inhibitor Download PDFInfo
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- CN100427413C CN100427413C CNB2005100718215A CN200510071821A CN100427413C CN 100427413 C CN100427413 C CN 100427413C CN B2005100718215 A CNB2005100718215 A CN B2005100718215A CN 200510071821 A CN200510071821 A CN 200510071821A CN 100427413 C CN100427413 C CN 100427413C
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Abstract
The present invention relates to a ternary synergistic corrosion inhibitor which is a compound water treatment agent by adopting polyaspartic acid (PASP) substances as main abtiscaling components. The present invention is mainly composed of the three parts of substances containing lone-pair electrons in molecular structures, substances capable of generating deposits on the surfaces of metals and substances with chelation action on the deposits, wherein the dosage of the substances containing lone-pair electrons in molecular structures (measured by the polyaspartic acid) is 5 to 50 mg/L, the dosage of zinc salts of the substances capable of generating deposits on the surfaces of metals (measured by zn<2+>) is 1 to 5 mg/L, and the dosage of 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA) of the substances with chelation action on the deposits is 5 to 50 mg/L. The ternary synergistic corrosion inhibitor (PASP-Zn<2+>-PBTCA) of the present invention has fine corrosion inhibiting and antiscaling effects without prefilming, and the corrosion rate of carbon steel in water added with the corrosion inhibitor can be reduced to 0.041 mm/a. In addition, the present invention also has the advantages of small dosage of chemical agents, favorable corrosion inhibiting and antiscaling performances, etc., and is applicable to the treatment of recirculating cooling water and the treatment of waste water.
Description
Technical field
The present invention relates to a kind of synergetic inhibiter, especially for treatment of cooling water and wastewater treatment, contain the trielement synergistic corrosion inhibitor of polyaspartic acid material.
Background technology
Synergistic Effect of Corrosion Inhibitors is meant and cooperates suitable inhibiter mixture that under the identical situation of inhibiter consumption its corrosion mitigating effect obviously surpasses the corrosion mitigating effect that each component is used separately.As far back as early 1950s, Synergistic Effect of Corrosion Inhibitors just has been found and has become the main foundation of inhibiter research and the exploitation of modern goods inhibiter.People find out far away that to the essence and the regularity of inhibition synergistic effect the exploitation of composite inhibiter is experimental substantially yet up to now.Is that the inhibiter of main component is that example: PASP is a kind of water-soluble polymers with scale inhibition performance with exploitation recently with poly aspartic acid (be called for short PASP), phosphorus element-containing not in its molecular structure, can not cause body eutrophication, biodegradable is good, is a kind of green polymer.Water treatment method based on PASP is the forward position of present water technology.The water treatment prescription that the PASP that is mainly used in the anti-corrosion, scale-inhibiting processing of recirculating cooling water system run duration at present is, for example: United States Patent (USP) " Scale corrosion inhibitingcomposition " (U.S.Pat.No.6,464,900,2002) provide a kind of prescription of forming by poly aspartic acid and a kind of water-soluble organic oligomer, preservative effect when the consumption of poly aspartic acid and water-soluble organic oligomer in this prescription is respectively 15.0mg/L and 10.0mg/L is best, getting its corrosion speed by the spin etching testing experiment is 6.1mpy, and its corrosion mitigating effect is not ideal enough." a kind of is the composite water disposal agent of host with the poly aspartic acid " (Chinese patent publication number CN 1323750A), providing a kind of is main scale inhibition composition with poly aspartic acid, with the sodium wolframate is the multi-functional inhibition of inhibiter and other auxiliary components and the composite water disposal agent of scale effect, the use of this water conditioner needs earlier pre-film treatment agent to be dropped in the water, pre-film was handled about 48 hours, and then dilution is transferred to concentration of treatment, and kept.The component and the content of water conditioner were poly aspartic acid 100～250mg/L when pre-film water was handled, tungstate 100～250mg/L, Trisodium Citrate 300～400mg/L, benzotriazole 0～10mg/L, zinc salt 0～4mg/L.After pre-film is handled 48h, the water conditioner concentration when transferring to normal processing, the component of water conditioner and content are poly aspartic acid 1～7mg/L during normal processing, tungstate 5～15mg/L, Trisodium Citrate 20～40mg/L, benzotriazole 0～2mg/L, zinc salt 0～3mg/L.This composite water disposal agent need could obtain good effect on the basis of pre-film, and pre-membrane process needs a large amount of fresh water displacement and discharge of wastewater.Common composite corrosion inhibitor all is the collaborative prescriptions based on synergistic effect, and its exploitation is experimental substantially, needs empirical technician and does very many tests, and adding " fortune " could success.
Summary of the invention
The corrosion inhibitor formula that the purpose of this invention is to provide a kind of trielement synergistic binding mode adopts this pattern can design and develop the good synergistic corrosion inhibitor of corrosion mitigating effect, can be used for recirculated cooling water and handles and wastewater treatment.
A kind of trielement synergistic corrosion inhibitor of the present invention, be to be the composite water disposal agent of main scale inhibition composition with the polyaspartic acid material, it is characterized in that, synergistic corrosion inhibitor mainly is made of following three parts: the material that contains lone-pair electron in (1) molecular structure: the polyaspartic acid material, and its consumption is counted 5～50mg/L with poly aspartic acid; (2) can generate sedimental material in the metallic surface: zinc salt, its consumption is with Zn
2+Count 1～5mg/L; (3) settling is had the material of sequestering action: 2-phosphonic acid butane-1,2,4-tricarboxylic acid (being called for short PBTCA), its consumption is 5～50mg/L.
The polyaspartic acid material that the present invention adopts is poly aspartic acid or polyaspartic acid salts.
The polyaspartic acid salts that the present invention adopts is the poly aspartic acid an alkali metal salt: poly (sodium aspartate) or poly-aspartic potassium.
The polyaspartic acid salts that the present invention adopts is the poly aspartic acid alkaline earth salt: calcium polyaspartate or poly aspartic acid magnesium.
The zinc salt that the present invention adopts is zinc sulfate, zinc chloride or zinc nitrate.
Inhibition synergy pattern of the present invention is absorption-deposition-chelating control, be that synergistic corrosion inhibitor component molecule is made up of three kinds of functional groups with absorption, deposition, sequestering action at least, adsorption functional group contains lone-pair electron to adsorb to the metallic surface and the formation adsorption film, deposition functional group can form settling in the metallic surface to strengthen adsorption film, and chelating functional group has sequestering action with controlling diaphragm thickness to settling.The synergistic corrosion inhibitor of designing and developing according to this pattern passes through corrosion test, can determine the best proportioning and the consumption of three kinds of inhibiter components.According to the synergy pattern, designed and developed PASP-Zn of the present invention
2+-PBTCA trielement synergistic corrosion inhibitor.
In the composition of trielement synergistic corrosion inhibitor of the present invention, the N atom in the PASP molecule contains lone-pair electron, can with the transition metal atoms Cheng Jian with sky d track, be adsorbed on the metallic surface and reach the protection metal purpose.Shown in the following reaction formula:
In the composition of trielement synergistic corrosion inhibitor of the present invention, Zn
2+Can with the OH on the negative electrode
-Effect generates insoluble Zn (OH)
2Deposited film, thus adsorption film strengthened.
O
2+4e+2H
2O→4OH
- Zn
2++2OH
-→Zn(OH)
2↓
In the composition of trielement synergistic corrosion inhibitor of the present invention, PBTCA is a pentabasic acid, energy and Zn
2+Form more stable title complex, thereby play the thickness of controlling diaphragm, making it infinitely to increase.
Under 20～60 ℃, contain PASP-Zn
2+The aqueous solution of-PBTCA trielement synergistic corrosion inhibitor contacts with the metallic surface, can play the effect that prevents corrosion and fouling.
At trielement synergistic corrosion inhibitor of the present invention and existing PASP is that the inhibiter of main component is compared, and the present invention has following characteristics:
(1) existing PASP prescription all is the collaborative prescriptions based on synergistic effect, and its exploitation is experimental substantially, needs empirical technician and does very many tests, and adding " fortune " could success.Synergy pattern of the present invention has tangible directive function to the exploitation of inhibiter, can significantly reduce blindness in the synergistic corrosion inhibitor research and development and empirical, significantly reduces test number (TN) and improves the working efficiency of inhibiter exploitation.
(2) existing PASP prescription need could obtain good effect on the basis of pre-film, and the fresh water that pre-membrane process need be a large amount of is replaced and discharge of wastewater, the PASP-Zn that designs and develops according to pattern provided by the invention
2+-PBTCA trielement synergistic corrosion inhibitor does not need pre-film can reach good anticorrosion-antiscaling effect, and advantage such as it is little to have a dosing, and corrosion and scale inhibition performance is good.With standard dynamic corrosion test method test, the corrosion speed of carbon steel in being added with the water of this inhibiter can be reduced to 0.041mm/a, be much better than Code for design of industrial recirculating cooling water treatment (GB50050-95) defined technical indicator (≤0.125mm/a).
Embodiment
Embodiment 1
Prescription according to the present invention is prepared water conditioner with conventional method.According to the HG/T2159-91 standard, standard A 3 steel test pieces are fixed on the test piece frame of dynamic corrosion tester, do not need pre-film to handle and directly put into and be added with PASP30mg/L, zinc chloride 3mg/L is (with Zn
2+Meter), in the test glass of PBCTA20mg/L and standard corrosive water (containing Calcium dichloride dihydrate 735mg/L, sal epsom 493mg/L, sodium-chlor 658mg/L and sodium bicarbonate 168mg/L), test glass places 40 ℃ water bath with thermostatic control, and test piece is with 0.35m.S
-1Rotating speed rotation, the test solution spontaneous evaporation replenishes a water every 4h, stops test behind the 72h, the corrosion speed that records standard A 3 steel test pieces is 0.050mm/a.
Embodiment 2
Working method is identical with embodiment 1, and poly (sodium aspartate) is substituted PASP (consumption is in PASP), and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.052mm/a.
Embodiment 3
Working method is identical with embodiment 1, and calcium polyaspartate is substituted PASP (consumption is in PASP), and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.056mm/a.
Embodiment 4
Working method is identical with embodiment 1, and zinc sulfate is substituted zinc chloride, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.054mm/a.
Embodiment 5
Working method is identical with embodiment 1, and zinc nitrate is substituted zinc chloride, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.053mm/a.
Embodiment 6
Working method is identical with embodiment 1, and the consumption of PASP is become 5mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.108mm/a.
Embodiment 7
Working method is identical with embodiment 1, and the consumption of PASP is become 50mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.042mm/a.
Embodiment 8
Working method is identical with embodiment 1, and the consumption of zinc chloride is become 1mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.078mm/a.
Embodiment 9
Working method is identical with embodiment 1, and the consumption of zinc chloride is become 5mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.046mm/a.
Embodiment 10
Working method is identical with embodiment 1, and the consumption of PBCTA is become 5mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.084mm/a.
Embodiment 11
Working method is identical with embodiment 1, and the consumption of PBCTA is become 50mg/L, and all the other conditions are identical with embodiment 1.The corrosion speed that records standard A 3 steel test pieces is 0.041mm/a.
Claims (5)
1. trielement synergistic corrosion inhibitor, be to be the composite water disposal agent of main scale inhibition composition with the polyaspartic acid material, it is characterized in that, synergistic corrosion inhibitor is made of following three parts: the material that contains lone-pair electron in (1) molecular structure: the polyaspartic acid material, and its consumption is counted 5～50mg/L with poly aspartic acid; (2) can generate sedimental material in the metallic surface: zinc salt, its consumption is with Zn
2+Count 1～5mg/L; (3) settling is had the material of sequestering action: 2-phosphonic acid butane-1,2,4-tricarboxylic acid, its consumption are 5～50mg/L.
2. synergistic corrosion inhibitor according to claim 1 is characterized in that, the polyaspartic acid material is poly aspartic acid or polyaspartic acid salts.
3. synergistic corrosion inhibitor according to claim 2 is characterized in that, polyaspartic acid salts is poly (sodium aspartate) or poly-aspartic potassium.
4. synergistic corrosion inhibitor according to claim 2 is characterized in that, polyaspartic acid salts is calcium polyaspartate or poly aspartic acid magnesium.
5. synergistic corrosion inhibitor according to claim 1 is characterized in that, zinc salt is zinc sulfate, zinc chloride or zinc nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100718215A CN100427413C (en) | 2005-05-25 | 2005-05-25 | Trielement synergistic corrosion inhibitor |
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| CNB2005100718215A CN100427413C (en) | 2005-05-25 | 2005-05-25 | Trielement synergistic corrosion inhibitor |
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| CN100427413C true CN100427413C (en) | 2008-10-22 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452726A (en) * | 2010-10-25 | 2012-05-16 | 上海丰信环保科技有限公司 | Preparation method of environmental protection low-phosphor composite scale and corrosion inhibitor |
| CN102344203B (en) * | 2010-12-14 | 2012-11-28 | 新疆德蓝股份有限公司 | High-temperature-resistant scale inhibitor for circulating water |
| CN103319006B (en) * | 2013-07-08 | 2016-07-06 | 广州市金润环保科技有限公司 | A kind of New Type Water Treatment Chemicals and preparation method thereof |
| CN103319011A (en) * | 2013-07-15 | 2013-09-25 | 北京市龙源科创石油技术有限公司 | Low-phosphorous environment-friendly composite scale and corrosion inhibitor |
| CN105217806A (en) * | 2015-10-13 | 2016-01-06 | 武汉钢铁(集团)公司 | Circulating water corrosion inhibitor and application thereof |
| CN106833527B (en) * | 2017-04-10 | 2019-05-07 | 中盐工程技术研究院有限公司 | A kind of high-efficiency environment friendly inhibition compounding deicing salt |
| CN111453862B (en) * | 2020-04-09 | 2023-01-06 | 成都纺织高等专科学校 | Multi-component compound corrosion inhibitor for magnesium and magnesium alloy and application method thereof |
| CN113800653A (en) * | 2020-06-16 | 2021-12-17 | 中国石油化工集团有限公司 | Geothermal fluid scale inhibitor and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0672625A1 (en) * | 1994-03-14 | 1995-09-20 | Bayer Ag | Compound for water treatment with polyaspartic acid or a derivative thereof and phosphonic acid |
| CN1323750A (en) * | 2001-06-19 | 2001-11-28 | 华东理工大学 | Composite water treating agent with polyasparagic acid as main component |
| CN1345696A (en) * | 2000-09-29 | 2002-04-24 | 中国石油化工股份有限公司 | Multi-function water treatment agent for circulating water cooling system |
| CN1603253A (en) * | 2003-09-29 | 2005-04-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Composite anti-dirty corrosion inhibiting agent and application thereof |
| WO2005097689A1 (en) * | 2004-04-01 | 2005-10-20 | Westinghouse Electric Company Llc | Improved scale conditioning agents and treatment method |
-
2005
- 2005-05-25 CN CNB2005100718215A patent/CN100427413C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0672625A1 (en) * | 1994-03-14 | 1995-09-20 | Bayer Ag | Compound for water treatment with polyaspartic acid or a derivative thereof and phosphonic acid |
| CN1345696A (en) * | 2000-09-29 | 2002-04-24 | 中国石油化工股份有限公司 | Multi-function water treatment agent for circulating water cooling system |
| CN1323750A (en) * | 2001-06-19 | 2001-11-28 | 华东理工大学 | Composite water treating agent with polyasparagic acid as main component |
| CN1603253A (en) * | 2003-09-29 | 2005-04-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Composite anti-dirty corrosion inhibiting agent and application thereof |
| WO2005097689A1 (en) * | 2004-04-01 | 2005-10-20 | Westinghouse Electric Company Llc | Improved scale conditioning agents and treatment method |
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