CN100587119C - Multifunctional hydrochloric acid pickling additive - Google Patents
Multifunctional hydrochloric acid pickling additive Download PDFInfo
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- CN100587119C CN100587119C CN200610124244A CN200610124244A CN100587119C CN 100587119 C CN100587119 C CN 100587119C CN 200610124244 A CN200610124244 A CN 200610124244A CN 200610124244 A CN200610124244 A CN 200610124244A CN 100587119 C CN100587119 C CN 100587119C
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- China
- Prior art keywords
- hydrochloric acid
- multifunctional
- acid pickling
- additive
- water
- Prior art date
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Abstract
The multifunctional hydrochloric acid pickling additive consists of polyoxyethylene ether or similar surfactant matter 1-10 %, active anion component 20-45 %, complexing agent 5-15 %, and water for the rest. It has the functions of retarding corrosion, inhibiting fog, promoting dissolution and preventing rust. It has the synergistic adsorption effect of both surfactant and active anion to form stable single molecular adsorption layer on the surface of the metal substrate to retard corrosion during pickling and prevent rust after cleaning; and the bubble and corrosion retarding layer the surfactant forms on the surface of the cleaning liquid to inhibit fog and avoid 'hydrogen embrittlement'. The components in the multifunctional hydrochloric acid pickling additive have low or no toxicity toensure the safety of the pickling process.
Description
Technical field
The invention belongs to steel product and material surface treatment industry technical field, be specifically related to a kind of multifunctional hydrochloric acid pickling additive.
Background technology
For realize steel product and material anticorrosion, decorate or other function, it is necessary processing means that the surface of steel product or material is handled, and steel product or material often pollute because of burn in manufacturing, processing, transportation, storage process or other reason etc., be covered with corrosion or dirt at steel surface, therefore, it is the surface-treated important step that metal products or material are cleaned, and cleaning quality and efficient are decision surface-treated key links.Hydrochloric acid is the surface cleaning liquid of using always, and it not only has stronger dissolving power to the corrosion of metallic surface, and the dirt of calcic, magnesium and so on is also had certain dissolving power.Because hydrochloric acid acidity is stronger, and has bigger volatility, often occur " crossing erosion " in the chlorohydric acid pickling process and reach " acid mist " phenomenon, cause that thus steel product and material matrix are corroded, not only waste lot of materials and luxus consumption scavenging solution, and cause the hydrogen that produces to produce " hydrogen embrittlement " phenomenon and influence the performance of material to the metallic matrix internal penetration, also can overflow because of acid mist cause the workshop air quality to be affected.For avoiding above-mentioned phenomenon, need to add restrainer in the chlorohydric acid pickling process, more representational hydrochloric acid pickling corrosion inhibitor has nitrogenous compound (as monoamine, diamines, acid amides, heterocyclic aromatic amine), aldehydes (as formaldehyde, phenylacrolein), sulfocompound (as thiocarbamide and derivative thereof), P contained compound (as tributyl phosphate, the ethylene glycol first and second basic di 2 ethylhexyl phosphonic acids) etc.Above-mentioned inhibiter mainly is to utilize nitrogen in the molecular structure, phosphorus, sulphur etc. for the polar group and the metallic surface atom formation coordinate bond of central atom chemisorption to take place; thereby form one deck unit molecule protective membrane in the metallic surface; hydrogen ion contacts with metallic matrix replacement(metathesis)reaction takes place in the prevention hydrochloric acid; reach the purpose of inhibition thus; also reduced the generation of hydrogen simultaneously, also reached and reduced the purpose that hydrochloric acid mist produces because of the minimizing of metallics and hydrogen ion generation replacement(metathesis)reaction.
Though present applied salt acid inhibitor has higher inhibition efficiency, ubiquity following shortcoming: 1) function singleness, a plurality of kinds of need are used just can reach the desired inhibition of cleaning, press down mist, promote the dissolved function; 2) toxicity is bigger, has safety problem in the use; 3) exist plant nutrient in the molecular structure, may cause the eutrophication of water body after the discharging; 4) clean and not possess antirust ability after finishing, the metallic matrix that exposes out is easy in air oxidized and produce corrosion once more, is unfavorable for follow-up surface treatment.
Summary of the invention
The objective of the invention is to utilize the synergy between surfactant and the active anion, provide a kind of and have inhibition, press down mist, promote the additive of dissolving and multiple function such as antirust, be convenient in the chlorohydric acid pickling process to realize the cleaning performance of efficient, cleaning, environmental protection, make the metal that is cleaned have higher smooth finish and resistance of oxidation, be convenient to follow-up surface treatment.
The corrosion of steel product and material surface is formed very complicated, but its composition mainly is FeO, Fe
2O
3, Fe
3O
4Deng the oxide compound of iron, when cleaning steel product and material with hydrochloric acid, with the corrosion on surface following reaction takes place mainly:
FeO+2HCl→FeCl
2+H
2O 1)
Fe
2O
3+6HCl→2FeCl
3+3H
2O 2)
Fe
3O
4+8HCl→FeCl
2+2FeCl
3+4H
2O 3)
When hydrochloric acid contacts with metallic matrix, also following corrosion reaction can take place:
Fe+2HCl→FeCl
2+H
2↑ 4)
After cleaning finished, the metallic matrix that exposes out had higher activity, contacted with airborne oxygen following series reaction can take place:
2Fe+O
2+2H
2O→2Fe(OH)
2 5)
Fe(OH)
2→FeO+H
2O 6)
4Fe(OH)
2+O
2+2H
2O→4Fe(HO)
3 7)
2Fe(OH)
3→Fe
2O
3+3H
2O 8)
Fe
2O
3+FeO→Fe
3O
4 9)
5)～9) be the chemical principle of iron and steel corrosion, but as long as stop reaction 5) generation, then can avoid follow-up 6)～9) corrosion reaction.
Multifunctional hydrochloric acid pickling additive provided by the present invention be for accelerate in cleaning process 1)～3) reaction, and suppress 4 simultaneously) generation of reaction, cleaning the molecular layer that is adsorbed on the metallic surface after finishing also can inhibited reaction 5) generation.Steel product and material chlorohydric acid pickling process are efficient in order to satisfy, cleaning, environmental protection and clean the antirust requirement in back, utilize the collaborative adsorption between surfactant and the active anion, form stable unimolecular layer in steel product that is cleaned and material surface, provide a kind of and have inhibition, press down mist, promote dissolving and multi-functional multifunctional hydrochloric acid pickling additive such as antirust.
It is main component that multifunctional hydrochloric acid pickling additive provided by the present invention adopts polyethenoxy ether class surfactant and active anion, with the complexing agent is that ancillary component combines, do not contain elements such as N, P, S in the molecular structure of above-mentioned substance, also the toxicological harmless composition is realized safety and environmental protection requirement in the use.
Know-why of the present invention has been to utilize the collaborative adsorption of polyoxyethylene ether surface active material and active anion, form stable unimolecular film in metal base surface generation chemisorption, stop the hydrogen ion in the pickle solution contact with metallic matrix, the generation of minimizing hydrogen and reach inhibition, but the purpose of mist.Have with oxygen in the molecular structure of the polyethenoxy ether class surfactant that adopts in the product of the present invention is the polar group and the alkyl non-polar group of central atom, it is well behaved tensio-active agent, have 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 this class surfactant belongs to nonionic surface active agent, not strong with the metallic surface atomic binding forces, the formation adsorption layer is insecure, though certain corrosion mitigating effect is arranged, but it is not very desirable, though Soxylat A 25-7 has stronger latherability, can form the foam layer of one deck densification on the scavenging solution surface to stop the effusion of hydrochloric acid mist, but owing to produced a large amount of hydrogen in the cleaning process, also can't suppress hydrochloric acid mist overflows together in company with hydrogen, therefore also but difficulty reaches preferably fog effect, and after the adding of active anion composition, can improve the stability of Soxylat A 25-7 molecule significantly in metal base surface absorption, can play the effect of stablizing monomolecular adsorption layer, thereby produce the obvious synergistic adsorption, stop metal to contact thus with hydrogen ion.
Polyethenoxy ether class surfactant of the present invention be meant with the oxyethane adduct number at 9～15 polyxyethylated alkylphenol
Active anion is meant I
-, Br
-Deng, the chemical of introducing active anion in the prescription of reality is its sylvite or sodium salt, and complexing agent is not for containing the citrate of N, S, P, and the actual material of introducing citrate is citric acid or its alkaline metal salt material, the Fe in citrate and the solution
2+, Fe
3+Complexation constant Deng free metal ion is respectively 15.5 and 25.0, can be preferentially and Fe
3+Form stable complex compound, promote the dissolving of surface corrosion, and be reduced in free Fe in the scavenging solution simultaneously
2+, Fe
3+Concentration is accelerated the dissolving of oxide on surface.
Concrete prescription of the present invention is:
Polyethenoxy ether class surfactant: 1～10%
Active anion composition: 20～45%
Complexing agent: 5～15%
Water: surplus.
One of screening formulation is polyoxyethylene Zhong Xin phenolic ether-12:3%, potassiumiodide: 30%, and citric acid: 6%, water: surplus.
Two of screening formulation is polyoxyethylene Zhong Xin phenolic ether-9:4%, Sodium Bromide: 30%, and Trisodium Citrate: 4%, water: surplus.
The additive of above-mentioned prescription and industrial hydrochloric acid are made into scavenging solution according to 1: 100 ratio.
When reality was used, hydrochloric acid was 18～25% industrial ortho acid, added this product 1% in the former acid solution per ton, can satisfy industry and clean needed inhibition, presses down mist, promotes dissolving and antirust effect.
Beneficial effect after the invention process is:
1, have inhibition, press down mist, promote the corrosion dissolving and clean the antirust function in back, can satisfy steel product hydrochloric acid and clean many-sided demand, the antirust function after particularly cleaning helps the follow-up surface treatment of metal products;
2, after sour molten reaction was suppressed, it was few to produce amounts of hydrogen, can suppress the generation of " hydrogen embrittlement " phenomenon;
3, do not contain compositions such as N, P, S in the formula for a product, finish cleaning after, waste liquid can not cause water surrounding the influence of eutrophication can not discharge S because of anaerobic reduction yet
2-Deng radioactive substance;
4, each component all belongs to low toxicity or nontoxic in the formula for a product, can satisfy safe requirement in the cleaning, and health of operators is not threatened;
Embodiment
For further specifying effect of the present invention, describe in conjunction with following example, but the present invention is not limited to following these examples.
Embodiment 1:
Polyoxyethylene Zhong Xin phenolic ether-9:4%
Sodium Bromide: 30%
Trisodium Citrate: 5%
Water: surplus.
Get the product of above-mentioned prescription and the scavenging solution that about 20% hydrochloric acid is made into 1: 100 during use, the cleaning tape product made from steel is through on probation, corrosion inhibition rate is 98.1%, pressing down the mist rate is 92.5%, improves cleaning speed 22%, and the band steel that cleans out is placed and do not produced rust staining in 5 hours.
Embodiment 2:
Polyoxyethylene Zhong Xin phenolic ether-10:10%
Potassiumiodide: 45%
Tripotassium Citrate: 15%
Water: surplus.
Get the additive of above-mentioned prescription and 25% hydrochloric acid during use and be made into scavenging solution, clean hardware, through on probation according to 1: 100 ratio, inhibition efficiency reaches 97.7%, pressing down the mist rate is 95.6%, improves cleaning speed 27%, and the hardware of clean is placed and do not produced rust staining in 12 hours.
Embodiment 3:
Polyoxyethylene Zhong Xin phenolic ether-12:3%
Potassiumiodide: 30%
Citric acid: 6%
Water: surplus.
Get the product of above-mentioned prescription and the scavenging solution that about 20% hydrochloric acid is made into 1: 100 during use, clean angle iron component, through on probation, corrosion inhibition rate reaches 98.5%, pressing down the mist rate is 90.6%, improves cleaning speed 25%, and the angle iron component that cleans out is placed and do not produced rust staining in 6 hours.
Embodiment 4:
Polyoxyethylene Zhong Xin phenolic ether-14:10%
Potassium Bromide: 20%
Tripotassium Citrate: 15%
Water: surplus.
Get the product of above-mentioned prescription and the scavenging solution that about 25% hydrochloric acid is made into 1: 100 during use, the test piece of cleaning tape steel is through on probation, corrosion inhibition rate reaches 96.8%, press down the mist rate and reach 93.7%, improve cleaning speed 29%, the band steel test piece that cleans out is placed and was not produced rust staining in 8 hours.
Embodiment 5:
Polyoxyethylene Zhong Xin phenolic ether-15:5%
Sodium Bromide: 30%
Trisodium Citrate: 8%
Water: surplus.
Get the product of above-mentioned prescription and the scavenging solution that about 20% hydrochloric acid is made into 1: 100 during use, the test piece of cleaning tape steel is through on probation, corrosion inhibition rate reaches 98.7%, press down the mist rate and reach 91.7%, improve cleaning speed 25%, the band steel test piece that cleans out is placed and was not produced rust staining in 6 hours.
Claims (4)
1, a kind of multifunctional hydrochloric acid pickling additive is characterized in that: this additive is made up of polyethenoxy ether class surfactant, active anion, complexing agent and water, and it is composed as follows to fill a prescription:
Polyethenoxy ether class surfactant: 1～10%
Active anion composition: 20～45%
Complexing agent: 5～15%
Water: surplus;
Above-mentioned polyethenoxy ether class surfactant be meant with the oxyethane adduct number at 9～15 polyxyethylated alkylphenol
Active anion is meant I-, Br
-, the chemical of introducing active anion in the prescription of reality be a kind of in its sylvite or the sodium salt, complexing agent is citric acid and the alkaline metal salt material thereof that does not contain N, S, P.
2, multifunctional hydrochloric acid pickling additive according to claim 1 is characterized in that: the polyoxyethylene Zhong Xin phenolic ether-12:3% of above-mentioned component, and potassiumiodide: 30%, citric acid: 6%, water: surplus.
3, multifunctional hydrochloric acid pickling additive according to claim 1 is characterized in that: the polyoxyethylene Zhong Xin phenolic ether-9:4% of above-mentioned component, and Sodium Bromide: 30%, Trisodium Citrate: 5%, water: surplus.
4, the application of the described multifunctional hydrochloric acid pickling additive of a kind of claim 1 is characterized in that: during actual the use, the additive of above-mentioned prescription and industrial hydrochloric acid are made into scavenging solution according to 1: 100 ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610124244A CN100587119C (en) | 2006-12-15 | 2006-12-15 | Multifunctional hydrochloric acid pickling additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610124244A CN100587119C (en) | 2006-12-15 | 2006-12-15 | Multifunctional hydrochloric acid pickling additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1974852A CN1974852A (en) | 2007-06-06 |
| CN100587119C true CN100587119C (en) | 2010-02-03 |
Family
ID=38125194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610124244A Expired - Fee Related CN100587119C (en) | 2006-12-15 | 2006-12-15 | Multifunctional hydrochloric acid pickling additive |
Country Status (1)
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|---|---|
| CN (1) | CN100587119C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101586243B (en) * | 2009-06-16 | 2011-05-18 | 武汉钢铁(集团)公司 | Hot rolled plate hydrochloric acid pickling corrosion inhibition accelerator |
| CN103233235B (en) * | 2013-05-16 | 2015-08-19 | 广东工业大学 | A kind of industrial acid-washed auxiliary agent and application thereof |
| CN104562056A (en) * | 2014-11-14 | 2015-04-29 | 无锡信大气象传感网科技有限公司 | Scale-rust removing agent for zinc-plated shell of sensor |
| CN104498969B (en) * | 2014-12-26 | 2017-12-19 | 湖南金裕化工有限公司 | Multi-functional pickling additive and preparation method thereof |
-
2006
- 2006-12-15 CN CN200610124244A patent/CN100587119C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 钢铁常温低浓度盐酸酸洗新工艺. 吴厚贵.电镀与涂饰，第16卷第2期. 1997 |
| 钢铁常温低浓度盐酸酸洗新工艺. 吴厚贵.电镀与涂饰，第16卷第2期. 1997 * |
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|---|---|
| CN1974852A (en) | 2007-06-06 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Assignee: Kaiping Sanwei Motor Ltd. Assignor: Guangdong University of Technology Contract record no.: 2011440000900 Denomination of invention: Multifunctional hydrochloric acid pickling additive Granted publication date: 20100203 License type: Exclusive License Open date: 20070606 Record date: 20110805 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20191215 |