CN103233235A - Industrial pickling assistant and application thereof - Google Patents
Industrial pickling assistant and application thereof Download PDFInfo
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- CN103233235A CN103233235A CN2013101816879A CN201310181687A CN103233235A CN 103233235 A CN103233235 A CN 103233235A CN 2013101816879 A CN2013101816879 A CN 2013101816879A CN 201310181687 A CN201310181687 A CN 201310181687A CN 103233235 A CN103233235 A CN 103233235A
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Abstract
The invention discloses an industrial pickling assistant and application thereof. The industrial pickling assistant is prepared from polyaspartic acid, polyoxyethylene ether surfactant, a complexing agent and water in a mixing manner; and the industrial pickling assistant and 18-25wt% of industrial sulfuric acid or hydrochloric acid are mixed to prepare into a cleaning solution according to the weight ratio of 1 to (100-150). The product disclosed by the invention utilizes the collaborative adsorption effect of polyaspartic acid and polyoxyethylene ether surfactant; a stable absorption layer can be stably formed at the surface of metallic matrix, so as to achieve the corrosion-inhibition and anti-rusting effects; the binding force of a rusting layer, a dirt layer and metallic matrix is reduced by utilizing permeating and wetting action of the surfactant; rapid dropping is facilitated; the metal complex ion is formed by the complex agent and Fe, Ca and Mg; free metal ions are reduced to achieve the target of facilitating dissolving of rusting of a steel product or material surface; the components are low in toxicity and biodegradable; and no adverse environmental consequences are generated after the industrial pickling assistant is used.
Description
Technical field
The invention belongs to technical fields such as surface treatment, environmental chemical engineering, material protection, be specifically related to a kind of industrial acid-washed auxiliary agent and application thereof.
Background technology
Ferrous materials is industrial production and social life material the most commonly used, but because it has higher chemically reactive, the normal surface corrosion that produces in production, transportation and storage process, and this corrosion layer is loosely organized, can not prevent airborne oxygen endosmosis, cause the further corrosion of material inside because bigger hygroscopic effect is arranged on the contrary.For realizing steel product and material surface is anticorrosion and decorate, must clean surperficial corrosion layer, be convenient to subsequent disposal to obtain comparatively clean Surface.The surface cleaning of ferrous materials strong acid commonly used is as scavenging solution, to dissolve the dirt of surperficial corrosion and calcic, magnesium and so on.Because acidic cleaning solution corrodibility is stronger, after corrosion is cleaned and is finished, the strong acid scavenging solution then reacts with metal matrix, waste lot of materials and luxus consumption scavenging solution, the hydrogen that produces influences the performance of material to metallic matrix internal penetration generation " hydrogen embrittlement " phenomenon, also overflowing because of acid mist simultaneously causes the workshop air quality to be affected.
For avoiding the phenomenon of above-mentioned invalid pickling, the acid cleaning process effect that adopts the method for adding restrainer to realize slowing down bite commonly used.Restrainer commonly used at present comprises organic inhibitor and metallic salt inhibiter.Organic inhibitor is to utilize the polar group of atom centered by nitrogen in the molecular structure, phosphorus, the sulphur etc. and metallic surface atom to form coordinate bond and adsorption takes place basically, form the continuous or discrete adsorption film of one deck in the metallic surface, thereby reach the purpose of inhibition; Metallic salt material inhibiter significant feature principle is mainly to utilize the oxidisability of high-valency metal to form passive film in the metallic surface or utilize some metal ion sterically hindered in the surface adsorption generation, to stop H
+Near the metallic surface, or reduce the electrode reaction activity site, or change double electrical layers and influence the dynamic process of electrochemical reaction, thereby erosion rate is reduced.
Though at present employed organic and metallic salt restrainer can reach more satisfactory inhibition efficiency, but ubiquity following not enough in the engineering application process: 1) only have corrosion inhibiting ability, after material surface forms stable protective membrane, equally also will protect schmutzband or corrosion layer, slow down pickling speed, influenced working efficiency; 2) the part component has certain toxicity, and residual material exists safety issue, also needs subsequent disposal can reach requirement on environmental protection simultaneously; 3) it is exposed fully to clean top layer, the back metal that finishes, and does not possess antirust ability, carries or the retention period is easy in air oxidizedly and produce corrosion again in two workshop sections, is unfavorable for follow-up surface treatment; 4) adaptive surface is comparatively narrow, can only use in single pickling system.
Summary of the invention
In production, processing, transportation and storage process, ferrous materials because of have higher activity in surface production oxidation corrosion layer or produce schmutzband because of the deposition of other material, its composition is very complicated, not only includes various oxide compounds (FeO, the Fe of Fe
2O
3, Fe
3O
4), Ca, Mg salt and SiO
2Deng, also contain the dirt of mineral oil and so on.The existence of above-mentioned substance, cause the top layer of ferrous materials to form the corrosion and the schmutzband that mix, corrosion and schmutzband are loosely organized, and have the effect of moisture absorption, dissolved oxygen, can form small chemical primary cell with the reactive metal matrix of bottom, can accelerate the corrosion of underlying metal matrix.The purpose of pickling is to adopt strong acid as the metal generation solubilizing reaction in scavenging solution and the top layer corrosion, makes the various oxide compounds of Fe, Ca, Mg produce water-soluble material, destroys the rock steady structure of corrosion layer and schmutzband, thereby reaches the purpose of clean surface.Pickle solution has stronger corrodibility, in case corrosion layer cleaning finish, thereby the reactive metal matrix of exposing then reacts with acidic cleaning solution and consumes metallic substance and scavenging solution, and has produced a large amount of spent pickle liquors.
Adding inhibiter in pickle solution is to alleviate scavenging solution to the common method of metal matrix corrosion, but existing inhibiter exists, and cleaning speed is slow, function singleness and the problem that exists environmental safety, for solving the existing existing deficiency of restrainer, and the diversified function of increase pickling additive, the object of the invention is to provide a kind of safe and reliable industrial acid-washed auxiliary agent that utilizes, be suitable for industrial strong acid commonly used as the needs of scavenging solution, a kind of industrial acid-washed assistant medicament of polyacid kind (comprising sulfuric acid, hydrochloric acid) that is suitable for that namely provides.
The present invention is the synergy of having utilized poly aspartic acid (PASP), polyethenoxy ether class tensio-active agent and complexing agent, realize industrial acid-washed process inhibition, promote infiltration, press down mist, interim antirust requirement, reach fast, the purpose of the corrosion of high-efficiency cleaning steel material surface and schmutzband.Concrete know-why is to have utilized the collaborative adsorption of poly aspartic acid and polyethenoxy ether class tensio-active agent; form stable protective membrane in metal base surface generation physical-chemical mixing and absorption; stop the hydrogen ion in the pickle solution contact with metallic matrix, reduce the generation of hydrogen and reach inhibition, promote infiltration, but mist, antirust purpose temporarily.
Poly aspartic acid (PASP) is high molecular polymer; have a plurality of amino, carbonyl and carboxyl in its molecular structure; be respectively hydrophilic and hydrophobic group; these groups can be realized oriented adsorption at steel material surface according to its hydrophilic and hydrophobic characteristic; particularly amino and Sauerstoffatom; they and elemental metals iron have good affinity interaction; can form stable adsorption layer on the matrix metal surface; to the avidity of metal oxide then a little less than, can play a protective role and the burning deposits yields is not protected elemental metals.The amphiphilic structure of PASP molecule has well wetting, bubble, osmosis, with can rapid permeability after the metallic contact of corrosion metal base surface under the corrosion layer, and the metallic surface played wetting effect, but because the PASP molecule is high molecular polymer, the molecular structure complexity, when adsorbing in the metallic surface because sterically hindered effect, the adsorption layer space that forms is bigger, adsorption layer is not fine and close, and after the micromolecular tensio-active agent adding, can insert in the gap of PASP molecular adsorption layer, remedy the defective that exists between the macromole adsorption layer, promote the perfect of metal base surface adsorption layer, thereby produce the obvious synergistic adsorption, stop metal to contact with hydrogen ion thus.In addition, the Fe of the complexing agent in the auxiliary agent and corrosion layer and schmutzband
2+, Fe
3+, Ca
2+, Mg
2+Form the complex compound of favorable solubility, can accelerate the dissolving of corrosion layer and schmutzband, improve cleaning speed.
A kind of industrial acid-washed auxiliary agent provided by the invention, formed by following weight percent by poly aspartic acid, polyethenoxy ether class tensio-active agent, complexing agent and water:
Poly aspartic acid: 15.0 ~ 25.0%
Polyethenoxy ether class tensio-active agent: 2.0 ~ 5.0%
Complexing agent: 5.0 ~ 15.0%
Water: surplus.
Above-mentioned poly aspartic acid has following molecular structure:
Above-mentioned polyethenoxy ether class tensio-active agent refer to the oxyethane adduct number 9 ~ 15 polyxyethylated alkylphenol (
).
Above-mentioned complexing agent is citric acid.
The present invention also provides a kind of application of described industrial acid-washed auxiliary agent, and the industrial sulphuric acid of above-mentioned industrial acid-washed auxiliary agent and 18 ~ 25 wt % or technical hydrochloric acid are made into scavenging solution by weight the mixed of 1:100～150.
Compare with existing restrainer, the present invention has following advantage and characteristics:
1, as industrial acid-washed auxiliary agent, multiple functional, not only have the corrosion inhibition of common acid pickling inhibitor, can also accelerate the dissolving of corrosion and schmutzband by promoting infiltration and the effect of complexing, improve pickling efficient, suppress acid mist and produce, and satisfy interim antirust requirement;
2, adaptation is wide, and the restriction that planted by acid is little, can be used with hydrochloric acid, sulfuric acid widely, and have result of use preferably simultaneously;
3, the various component environmental safeties in the formula for a product are good, after finishing using, realize biological degradation easily, do not produce the residual substance of toxic;
4. utilized the collaborative adsorption of poly aspartic acid and polyethenoxy ether class tensio-active agent; form stable protective layer in metal base surface generation chemisorption; stop the hydrogen ion in the pickle solution to contact with metallic matrix; slow down the corrosion of strong acid; reach inhibition, press down the purpose of mist, utilize the ion of complexing agent and Fe, Ca, Mg to form the quick dissolving of stable comple promotion corrosion and dirt simultaneously.
5. this product has inhibition simultaneously, presses down mist, promotes dissolving and interim antirust function, and can be used with industrial acids kinds commonly used such as sulfuric acid, hydrochloric acid.
Embodiment
The present invention is further described below in conjunction with case study on implementation, but does not limit the present invention.(annotate: following ratio all is weight percentage)
Embodiment 1:
Poly aspartic acid: 16.0%
Polyoxyethylene Zhong Xin phenolic ether-9:2.0%
Citric acid: 7.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 25% industrial sulphuric acid is made into 1:150 during use, clean the plain carbon stool product, through on probation, corrosion inhibition rate is 98.7%, press down mist rate 81.6%, improve cleaning speed 19%, the plain carbon stool product that cleans out is placed and was not produced rust staining in 10 hours.
Embodiment 2:
Poly aspartic acid: 20.0%
Polyoxyethylene Zhong Xin phenolic ether-12:4.0%
Citric acid: 10.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 22% industrial sulphuric acid is made into 1:130 during use, clean the medium carbon steel member, through on probation, corrosion inhibition rate reaches 96.7%, press down mist rate 84.2%, improve cleaning speed 23%, the medium carbon steel member that cleans out is placed and was not produced rust staining in 10 hours.
Embodiment 3:
Poly aspartic acid: 25.0%
Polyoxyethylene Zhong Xin phenolic ether-15:5.0%
Citric acid: 15.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 20% industrial sulphuric acid is made into 1:120 during use, clean iron and steel handware product, through on probation, corrosion inhibition rate is 98.1%, press down mist rate 83.3%, improve cleaning speed 16%, the iron and steel handware product that cleans out is placed and was not produced rust staining in 11 hours.
Embodiment 4:
Poly aspartic acid: 17.0%
Polyoxyethylene Zhong Xin phenolic ether-9:3%
Citric acid: 6.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 20% technical hydrochloric acid is made into 1:100 during use, the cleaning tape steel bar, through on probation, corrosion inhibition rate reaches 97.1%, presses down mist rate 93.6%, improves cleaning speed 24%, and the band steel bar that cleans out is placed and was not produced rust staining in 4 hours.
Embodiment 5:
Poly aspartic acid: 21.0%
Polyoxyethylene Zhong Xin phenolic ether-12:4.0%
Citric acid: 11.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 18% technical hydrochloric acid is made into 1:130 during use, clean the angle steel product, through on probation, corrosion inhibition rate is 99.2%, presses down mist rate 93.4%, improves cleaning speed 22%, and the angle steel that cleans out is placed and do not produced rust staining in 6 hours.
Embodiment 6:
Poly aspartic acid: 24.0%
Polyoxyethylene Zhong Xin phenolic ether-15:5.0%
Citric acid: 14.0%
Water: surplus
Get the product of above-mentioned prescription and the scavenging solution that 20% technical hydrochloric acid is made into 1:150 during use, clean the soft steel member, through on probation, corrosion inhibition rate reaches 96.5%, press down mist rate 95.4%, improve cleaning speed 22%, the soft steel member that cleans out is placed and was not produced rust staining in 8 hours.
Claims (5)
1. industrial acid-washed auxiliary agent is characterized in that: be made up of by following weight percent poly aspartic acid, polyethenoxy ether class tensio-active agent, complexing agent and water:
Poly aspartic acid: 15.0 ~ 25.0%
Polyethenoxy ether class tensio-active agent: 2.0 ~ 5.0%
Complexing agent: 5.0 ~ 15.0%
Water: surplus.
2. industrial acid-washed auxiliary agent as claimed in claim 1, it is characterized in that: above-mentioned poly aspartic acid has following molecular structure:
3. industrial acid-washed auxiliary agent as claimed in claim 1 is characterized in that: above-mentioned polyethenoxy ether class tensio-active agent refer to the oxyethane adduct number 9 ~ 15 polyxyethylated alkylphenol (
).
4. industrial acid-washed auxiliary agent as claimed in claim 1, it is characterized in that: above-mentioned complexing agent is citric acid.
5. the application of the described industrial acid-washed auxiliary agent of claim 1 is characterized in that: the industrial sulphuric acid of above-mentioned industrial acid-washed auxiliary agent and 18 ~ 25 wt.% or technical hydrochloric acid are made into scavenging solution by weight the mixed of 1:100～150.
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|---|---|---|---|
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| CN201310181687.9A CN103233235B (en) | 2013-05-16 | 2013-05-16 | A kind of industrial acid-washed auxiliary agent and application thereof |
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| CN103233235B CN103233235B (en) | 2015-08-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568297A (en) * | 2015-12-21 | 2016-05-11 | 青岛农业大学 | Environment-friendly carbon steel pickling inhibitor and application thereof |
| CN107338444A (en) * | 2017-06-14 | 2017-11-10 | 广东红日星实业有限公司 | A kind of Novel hot-rolled steel cleaning agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1136089A (en) * | 1997-07-17 | 1999-02-09 | Kurita Water Ind Ltd | Pickling solution for stainless steel |
| CN1974852A (en) * | 2006-12-15 | 2007-06-06 | 广东工业大学 | Multifunctional hydrochloric acid pickling additive |
| CN101994124A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | Heterocyclic carbon steel pickling corrosion inhibitor and application thereof |
| CN101994122A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | Antibiotic carbon steel pickling corrosion inhibitor and application thereof |
-
2013
- 2013-05-16 CN CN201310181687.9A patent/CN103233235B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1136089A (en) * | 1997-07-17 | 1999-02-09 | Kurita Water Ind Ltd | Pickling solution for stainless steel |
| CN1974852A (en) * | 2006-12-15 | 2007-06-06 | 广东工业大学 | Multifunctional hydrochloric acid pickling additive |
| CN101994124A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | Heterocyclic carbon steel pickling corrosion inhibitor and application thereof |
| CN101994122A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | Antibiotic carbon steel pickling corrosion inhibitor and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| M.ZERFAOUI,ET AL.，: ""Inhibition of corrosion of iron in citric acid media by aminoacids"", 《PROGRESS IN ORGANIC COATINGS》, 31 December 2004 (2004-12-31) * |
| 许奕春等: ""绿色聚天冬氨酸复配缓蚀剂对A3碳钢的缓蚀抑雾作用"", 《物理化学学报》, vol. 26, no. 5, 31 May 2010 (2010-05-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568297A (en) * | 2015-12-21 | 2016-05-11 | 青岛农业大学 | Environment-friendly carbon steel pickling inhibitor and application thereof |
| CN107338444A (en) * | 2017-06-14 | 2017-11-10 | 广东红日星实业有限公司 | A kind of Novel hot-rolled steel cleaning agent and preparation method thereof |
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|---|---|
| CN103233235B (en) | 2015-08-19 |
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