CN1144899C - Acid mist inhibitor for hydochloric acid pickling, and its prodn. method - Google Patents
Acid mist inhibitor for hydochloric acid pickling, and its prodn. method Download PDFInfo
- Publication number
- CN1144899C CN1144899C CNB991132491A CN99113249A CN1144899C CN 1144899 C CN1144899 C CN 1144899C CN B991132491 A CNB991132491 A CN B991132491A CN 99113249 A CN99113249 A CN 99113249A CN 1144899 C CN1144899 C CN 1144899C
- Authority
- CN
- China
- Prior art keywords
- acid
- pickling
- toluquinoline
- hydochloric
- acid pickling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000002253 acid Substances 0.000 title claims abstract description 33
- 238000005554 pickling Methods 0.000 title claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003112 inhibitor Substances 0.000 title claims abstract description 15
- 101100006584 Mus musculus Clnk gene Proteins 0.000 title claims description 23
- 239000003595 mist Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title description 6
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 polyoxyethylene nonyl phenol Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 5
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 abstract 2
- 150000008051 alkyl sulfates Chemical class 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention provides a fog corrosion inhibitor for hydrochloric acid pickling, and a production method thereof. The product is mainly prepared from polyoxyethylene nonyl phenol ether, alkyl sulfate, methyl quinoline, oxidation tertiary amine, carboxymethyl cellulose and water, and has favorable fog inhibition performance and suitable corrosion inhibition performance. The inhibitor can effectively prevent acid fog from overflowing, and avoid the occurrence of metal base body over-pickling and hydrogen embrittlement phenomena. The fog corrosion inhibitor is an optimal fog corrosion inhibitor for hydrochloric acid pickling especially large-sized pickling machine sets with a waste acid desilication and regeneration system.
Description
The invention belongs to field of fine chemical, particularly a kind of large-scale chlorohydric acid pickling unit that has a spent acid desiliconization regeneration system rapidly is suitable for presses down mist inhibiter and production method.
In field of metallurgy press working industry, it is one requisite operation that cleanup acid treatment is carried out on the surface of steel.Along with the development of metallurgical technology, it is more and more obvious to replace the trend of sulfuric acid washing with chlorohydric acid pickling in acid cleaning process, and chlorohydric acid pickling also develops into the shallow slot pickling by the deep trouth pickling of beginning, and progressively develops into super shallow slot pickling and turbulent flow pickling.Meanwhile, spent acid is handled also tremendous development, ferrous to reclaiming from initial neutralizing treatment, so that manipulation of regeneration reclaims hydrochloric acid and brown iron oxide.Late nineteen eighties develops into again spent acid is carried out the desiliconization processing, reclaims hydrochloric acid and high-purity iron oxide red, and the latter is as electromagnetic material.And be that sulfuric acid washing or chlorohydric acid pickling all need restrainer, this is well-known.At present, existing both at home and abroad hundreds of kind and even thousands of kinds of inhibiter use in circulation, and its corrosion mitigating effect does not wait.The corrosion inhibition rate that has is up to 99.5%, and it is also fine to press down fog effect; What have presses down the mist rate and can reach more than 95%.But these inhibiter all can not be applicable to the chlorohydric acid pickling unit of the band spent acid desiliconization regeneration system rapidly that the nineties grows up.This unit requires to press down the corrosion inhibition rate of mist inhibiter can only be in 10%～30% scope, and material can not blocking pipeline, nozzle, not ectocrine mobile equilibrium and desiliconization regeneration unit operation.For example: the patent No. is disclosed a kind of iron and steel corrosion-retarding fog inhibitor and a production method thereof in the CN1093125A document, and this kind product only is applicable to sulfuric acid washing; The disclosed a kind of acid mist inhibitor for hydochloric acid pickling that is mixed with plant alkali salt and low quantity of surfactant in the CN1039269A patent documentation, corrosion inhibition rate reaches 95%, presses down the mist rate more than 80%.The corrosion inhibition of the said products all can not satisfy the service requirements of the chlorohydric acid pickling unit of band spent acid desiliconization regeneration system rapidly.
The objective of the invention is to provide a kind of certain inhibition scope that has that is applicable to band spent acid desiliconization regeneration system rapidly in order to overcome the deficiencies in the prior art, the good mist performance that presses down, not blocking pipeline, nozzle, the not acid mist inhibitor for hydochloric acid pickling of ectocrine mobile equilibrium and production method.
Product of the present invention is that the employing carbon chain lengths is 5～15 alkyl-sulphate (ROSO
3Na) and the oxyethane adduct number be 5～15 polyoxyethylene nonylphenol ether (
) as main component, toluquinoline is as submember, and employing tertiary amine oxide (RN (CH
3)
2) as suds-stabilizing agent, carboxymethyl cellulose (C
6H
9O
4OCH
2COOH)
nPerhaps molecular weight is the cationic-type polyacrylamide (C more than 1,000 ten thousand
3H
5NO)
nFor the dispersion agent of representing combines.Concrete prescription is:
Polyoxyethylene nonylphenol ether 0.1%～10%
C
5～C
15Alkyl-sulphate 0.2%～15%
Toluquinoline 0.01%～5%
Tertiary amine oxide 0.01%～1%
Carboxymethyl cellulose 0.001%～1%
Water surplus
Among the present invention, alkyl-sulphate has abundant foam in the aqueous solution, and can adjust corrosion inhibition rate, and the existing certain rust inhibition of polyoxyethylene nonylphenol ether can produce careful stable foam again; The residue itself that coal tar extracts behind benzene, the phenol just has certain corrosion inhibition, but owing to there is more neutral oil, influences its use, after acidification solubilized, be scattered in the water.Its main component is: 2-toluquinoline, 8-toluquinoline, isoquinoline 99.9 etc.
In the chlorohydric acid pickling operation, main purpose is to remove the iron scale of steel surface, and its reaction formula is:
By above-mentioned reaction formula as can be seen, make the matrix metal excessive erosion and produce acid mist and caused by reaction (4), therefore, the present invention reaches on the acid solution surface by the speed of response of adding tensio-active agent control reaction (4) step in pickling and forms evenly, and fine and close foam presses down mist inhibition purpose thereby reach.
The principle of work of spent acid desiliconization regeneration system rapidly is: (HCl 8%～12%, FeCl with used low-concentration hcl
2100g/l～120g/l; PH0.5～1) is transported to the desiliconization treatment tank, uses in scrap iron sheet and the ammoniacal liquor and spent acid solution, make pH value rise to 5.Make part Fe by air
2+Be converted into Fe (OH)
2And Fe (OH)
3Simultaneously, in treatment solution, add flocculation agent, make the oxyhydroxide deposition of iron take SiO out of
2Thereby realize the desiliconization purpose.If the corrosion inhibition rate that presses down the mist inhibiter that adds in acid solution is too high, then will influence the speed of response of this N-process, the manipulation step that makes whole desiliconization system lag behind whole process chlorohydric acid pickling line gathers, thereby influences the material balance of total system.This shows that it is relatively more suitable that the inhibition efficiency that presses down the mist inhibiter is controlled in 10%～30% scope.
The production technique of product of the present invention is: dilute, dissolve earlier each component in the prescription respectively, add toluquinoline, carboxymethyl cellulose, tertiary amine oxide successively afterwards in the water that fills required solution 2/3rds volumes, fully stir; Add polyoxyethylene nonylphenol ether, alkyl-sulphate again, stirring gets final product.
The present invention compares with prior art has following advantage;
1, overpickling and hydrogen embrittlement phenomenon have been prevented effectively.Unit stops for some reason, can not will in 30 minutes pickle solution enter storage acid jar, will steel band do not provoke being exposed on the acid solution liquid level yet.In processing condition is under HCl 200g/l, the 80 ℃ of conditions, meets above-mentioned situation and guarantees not overpickling, does not produce the hydrogen embrittlement phenomenon.
2, prevent that effectively acid mist is excessive, improved Working environment, guarantee that the motor long-term safety operation of pickling workshop contacts well with Controlling System.Prevent the principal element that acid mist is excessive: the one, because corrosion inhibition reduces the bubble hydrogen of carrying acid solution secretly of generation; The 2nd, the acid solution surface has the fine and closely woven stable foam of one deck to cover excessive acid mist.
3, effectively reduce sour consumption and the loss of minimizing matrix metal in acid cleaning process.
The present invention is described in further detail below in conjunction with embodiment.
Prepare one group of acid mist inhibitor for hydochloric acid pickling according to prescription provided by the invention and production method, its concrete prescription is:
Polyoxyethylene nonylphenol ether 8%
C
5～C
15Alkyl-sulphate 13%
Toluquinoline 4%
Tertiary amine oxide 3%
Carboxymethyl cellulose 0.5%
Deionized water 71.5%
The present invention is on probation on the chlorohydric acid pickling unit of the first band desiliconization regeneration system rapidly in the world, achieve good results.The throughput of this unit pickling part is 880,000 tons/year, regeneration section comprise soak molten, desiliconization, concentrate, system such as roasting, processing power is 2 * 5.5m
3/ h regenerating acid.Its result of use is after tested: press down mist rate 90.5%, corrosion inhibition rate 19.3% all reaches perfect condition.Tried out since 18 months, do not find pipeline, nozzle, interchanger, filter stoppage and ectocrine mobile equilibrium phenomenon, not only improved Working environment, and improved lumber recovery, economic benefit and social benefit be highly significant all.
Claims (5)
1, a kind of acid mist inhibitor for hydochloric acid pickling, it is characterized in that: with alkyl-sulphate and oxyethane adduct number is that 5～15 polyoxyethylene nonylphenol ether is as main component, toluquinoline is a submember, with tertiary amine oxide as stablizer, carboxymethyl cellulose or molecular weight are that the cationic-type polyacrylamide more than 1,000 ten thousand is that the dispersion agent of representative combines, and concrete prescription is:
Polyoxyethylene nonylphenol ether 0.1%～10%
C
5～C
15Alkyl-sulphate 0.2%～15%
Toluquinoline 0.01%～5%
Tertiary amine oxide 0.01%～1%
Carboxymethyl cellulose 0.001%～1%
Water surplus.
2, a kind of acid mist inhibitor for hydochloric acid pickling according to claim 1 is characterized in that toluquinoline is the product after coal tar extracts benzene, phenol.
3, a kind of acid mist inhibitor for hydochloric acid pickling according to claim 1 is characterized in that the water that adopts is deionized water.
4, a kind of acid mist inhibitor for hydochloric acid pickling according to claim 1 and 2 is characterized in that coal tar extracts residue behind benzene, the phenol as submember, and its main component is: 2-toluquinoline, 8-toluquinoline, isoquinoline 99.9.
5, according to the production method of a kind of acid mist inhibitor for hydochloric acid pickling of one of claim 1～4, it is characterized in that: dilute, dissolve earlier each component in the prescription respectively, in the water that fills required solution 2/3rds volumes, add toluquinoline, carboxymethyl cellulose, tertiary amine oxide successively afterwards, fully stir, add polyoxyethylene nonylphenol ether again, alkyl-sulphate, stirring gets final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991132491A CN1144899C (en) | 1999-09-14 | 1999-09-14 | Acid mist inhibitor for hydochloric acid pickling, and its prodn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991132491A CN1144899C (en) | 1999-09-14 | 1999-09-14 | Acid mist inhibitor for hydochloric acid pickling, and its prodn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288076A CN1288076A (en) | 2001-03-21 |
| CN1144899C true CN1144899C (en) | 2004-04-07 |
Family
ID=5276457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991132491A Expired - Fee Related CN1144899C (en) | 1999-09-14 | 1999-09-14 | Acid mist inhibitor for hydochloric acid pickling, and its prodn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1144899C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824624A (en) * | 2010-05-04 | 2010-09-08 | 武汉钢铁(集团)公司 | Hot-rolled plate chlorohydric acid pickling fog-resistant accelerator |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411981C (en) * | 2006-04-21 | 2008-08-20 | 华北电力大学（北京） | Burner for synthesizing nanometer carbon pipe by V type and conical type pyrolytic flame and its synthesizing method |
| 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 |
| CN101818352B (en) * | 2010-01-25 | 2011-08-24 | 夏光甫 | Strong acid fog inhibitor and preparation method thereof |
| CN101838813B (en) * | 2010-05-07 | 2011-11-09 | 天津惠邦同成科技发展有限公司 | Pickling-rinsing additive and preparation method thereof |
| CN101851761B (en) * | 2010-06-28 | 2011-06-15 | 遵义航天娄山电器化工有限公司 | Sulfuric acid washing corrosion-retarding fog inhibitor and preparation method thereof |
| CN106868518A (en) * | 2017-03-27 | 2017-06-20 | 刘雄杰 | Environment-friendly type hydrochloric acid cleans corrosion-retarding fog inhibitor |
| CN108315743B (en) * | 2018-03-02 | 2019-09-06 | 武汉华科特新技术有限公司 | A kind of preparation method of ergometrine restrainer |
-
1999
- 1999-09-14 CN CNB991132491A patent/CN1144899C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824624A (en) * | 2010-05-04 | 2010-09-08 | 武汉钢铁(集团)公司 | Hot-rolled plate chlorohydric acid pickling fog-resistant accelerator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288076A (en) | 2001-03-21 |
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Address after: 114009, No. 63, Wuyi Road, MTR Eastern District, Liaoning, Anshan Patentee after: ANGANG STEEL COMPANY LIMITED Address before: 114009, No. 63, Wuyi Road, MTR Eastern District, Liaoning, Anshan Patentee before: Angang New Steel Co.,Ltd. |
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