CN102154654A - Acid washing corrosion inhibitor - Google Patents
Acid washing corrosion inhibitor Download PDFInfo
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- CN102154654A CN102154654A CN 201110122663 CN201110122663A CN102154654A CN 102154654 A CN102154654 A CN 102154654A CN 201110122663 CN201110122663 CN 201110122663 CN 201110122663 A CN201110122663 A CN 201110122663A CN 102154654 A CN102154654 A CN 102154654A
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- corrosion inhibitor
- quaternary ammonium
- ammonium salt
- mixed alkyl
- acid washing
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Abstract
The invention discloses an acid washing corrosion inhibitor, which is characterized by comprising the following components in percentage by weight: 30 to 70 percent of mixed alkyl pyridine quaternary ammonium salt, 25 to 50 percent of alcohol, 1 to 4 percent of nonionic surfactant and the balance of water. Compared with the prior art, the acid washing corrosion inhibitor has the advantages that: a pharmaceutical byproduct is mixed with alkyl pyridine to perform modification so as to research the corrosion inhibitor; the acid washing corrosion inhibitor has higher water solubility; the corrosion inhibition effect of the acid washing corrosion inhibitor is superior to that of the common aldehyde ketone amine type corrosion inhibitor; the application temperature range of the acid washing corrosion inhibitor is wider than that of the aldehyde ketone amine type corrosion inhibitor; the aldehyde ketone amine type corrosion inhibitor is easy to carbonize under the condition of high temperature, so that the corrosion inhibition effect is influenced; and in addition, the acid washing corrosion inhibitor is lower in production cost compared with the aldehyde ketone amine type corrosion inhibitor, has a simple production process, has no generation of three wastes (waste water, waste gas and industrial residues) and meets the requirement for environmental friendliness.
Description
Technical field
The present invention relates to a kind of metallic surface clean technical field, especially refer to handle a kind of restrainer of carbon steel material and equipment pickling.
Background technology
The corrosion of strong acid clean surface, dirt are the important cleaning means of metal material surface pre-treatment, pipeline and the scale removal of boiler systems cleaning, so far still at metallic substance, and machinery, electric power, industries such as chemical industry have purposes widely.Because the corrodibility of strong acid, the phenomenon that often occurred erosion in the acid cleaning process, promptly in the process of cleaning, not only removed surperficial corrosion and dirt, also metal base is partly washed off together simultaneously, so acid cleaning process has caused the significant wastage of metallic substance and pickle solution.Also produce a large amount of spent pickle liquors simultaneously, caused the serious environmental pollution.Therefore, reduce the generation of spent pickle liquor from the source, be not only the needs that reduce production costs, important meaning is more arranged for reducing pollution load.And add inhibiter be address this problem very effectively and also use way very widely.
Since first restrainer patent was announced in 1860, the inhibiter that is applied to iron at present mainly is divided into and contains oxygen, nitrogen, sulphur, phosphorus compound inhibiter, or its composite deutero-new variety, mainly comprise amine, Thiourea, aldoketones, imidazolines, pyridine and quinoline quaternary ammonium salt, assorted polyamines class, wherein amine, aldoketones, pyridine and quinoline quaternary ammonium salt are used more aborning.Its corrosion mitigating effect is good.But from producing originally, the inhibiter of aldehyde ketone amine all will be through complicated building-up process, and production cost is higher, and production process can produce the three wastes, contaminate environment.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of to utilize medical byproduct mixed alkyl pyridine to carry out modification to handle and have that corrosion mitigating effect is good, production cost is low, technology is simple and free of contamination a kind of restrainer at above-mentioned prior art present situation.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this restrainer is characterized in that comprising following component, mixed alkyl pyridine quaternary ammonium salt 30～70%, alcohol 25～50%, nonionogenic tenside 1～4%, surplus is a water, more than is weight percentage.
As improvement, described mixed alkyl pyridine quaternary ammonium salt has following structure:
Wherein R is a substituting group, and R is Benzyl Chloride or propenyl chloride or epoxy chloropropane or p-chloromethyl styrene or ethylene dibromide, and wherein R ' is the C in ortho position or a position or the contraposition on the pyridine ring
1～C
3Alkyl.
Improve, described alcohol can be preferably methyl alcohol or ethanol or Virahol again.
Improve, described nonionogenic tenside can be preferably alkylphenol polyoxyethylene or peregal again.
Improve, described component can be preferably mixed alkyl pyridine quaternary ammonium salt 40～60% again, alcohol 35～55%, nonionogenic tenside 1～2%.
Improve again, the making method of described mixed alkyl pyridine quaternary ammonium salt is: mixed alkyl pyridine and quaternizing agent are according to molar ratio 1.1～2.5: 1, in the presence of 20-60% alcohol, control reaction temperature was reacted in 60-120 ℃ container backflow 4-16 hour, promptly obtain the mixed alkyl pyridine quaternary ammonium salt, the be preferably methyl alcohol of described 20-60% alcohol or ethanol or Virahol etc.
Compared with prior art, the invention has the advantages that: 1, utilize medical byproduct mixed alkyl pyridine to carry out the modification processing and be developed into inhibiter, it is water-soluble good, and the inhibiter of the aldehyde ketone amine that corrosion mitigating effect is used always is good; And its use temperature scope is wider than the inhibiter of aldehyde ketone amine, and the inhibiter of aldehyde ketone amine than charing easily under the condition with higher, has influenced corrosion mitigating effect in temperature; Also have, its production cost is cheap than the aldehyde ketone amine inhibitor, and production technique is simple, and the no three wastes produce, compliance with environmental protection requirements; 2, adopt the mixed alkyl pyridine quaternary ammonium salt corrosion inhibitor formula 0.3% that does not add synergistic agent, 15%HCl, under 60 ℃ of conditions, corrosion mitigating effect reaches 99%.And when reaching similar corrosion mitigating effect, mixed alkyl pyridine quaternary ammonium salt inhibiter requirement lacks 50% than the aldehyde ketone amine inhibitor.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The restrainer of present embodiment comprises following component, mixed alkyl pyridine quaternary ammonium salt 30～70%, and alcohol 25～50%, nonionogenic tenside 1～4%, surplus is a water, more than is weight percentage.Described alcohol is methyl alcohol or ethanol or different third or water/alcohol or polar solvent etc.Described nonionogenic tenside is alkylphenol polyoxyethylene or peregal.
The making method of this mixed alkyl pyridine quaternary ammonium salt is: mixed alkyl pyridine and quaternizing agent are according to molar ratio 1.1～2.5: 1, in the presence of 20-60% alcohol, control reaction temperature was reacted in 60-120 ℃ container backflow 4-16 hour, promptly obtain the mixed alkyl pyridine quaternary ammonium salt, the be preferably methyl alcohol of described 20-60% alcohol or ethanol or Virahol etc.Mixed alkyl pyridine quaternary ammonium salt of the present invention has following structure:
Wherein R is the substituting group that replaces H in the N position, and R is Benzyl Chloride or propenyl chloride or epoxy chloropropane or p-chloromethyl styrene or ethylene dibromide, and wherein R ' is the C in ortho position or a position or the contraposition on the pyridine ring
1～C
3Alkyl.
Inhibiter of the present invention also can comprise imidazolines and quinoline quaternary ammonium compound, perhaps synergistic agent propiolic alcohol, Na
2S and KI.
The working concentration of inhibiter of the present invention in hydrochloric acid-carbon steel and sulfuric acid-carbon steel system can be 0.07%～0.7%, preferred 0.3%～0.6%.
The invention will be further described below by embodiment;
Embodiment 1
The preparation of present embodiment inhibiter;
Get the 500ml four-hole boiling flask, add mixed alkyl pyridine 100g, ethanol or methyl alcohol 80g stir, are heated to about 80 ℃, and backflow 0.5h (h refers to the unit of time hour, promptly refers to English hour, and is as follows) makes the mixed alkyl pyridine fully be dissolved in the ethanol; Dissolving finishes, drip then about Benzyl Chloride 70g, the dropping time is 0.5～1h, dropwises, and control reaction temperature continues about stirring and refluxing reaction 8-12h at 80 ℃, obtain brown oily liquid to black, promptly be prepared into the mixed alkyl pyridine quaternary ammonium salt, added the nonionogenic tenside OP-10 (OP-10 refers to alkylphenol polyoxyethylene, and is as follows) of 5g then, stir, promptly be prepared into the inhibiter of mixed alkyl pyridine quaternary ammonium salt.
Can prepare different mixed alkyl pyridine quaternary ammonium salt inhibiter with different quaternizing agent halogenide and mixed alkyl pyridine.The dosage of used single agent all calculates by pure product, down together.
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in following table 1, table 2.
Embodiment 2
Inhibiter is formed: mixed alkyl allyl pyridine quaternary ammonium salt 50g,, 1g nonionogenic tenside OP-10,
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
Embodiment 3
Inhibiter is formed: mixed alkyl propylene oxide yl pyridines quaternary ammonium salt 50g, the nonionogenic tenside OP-10 of 1g
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
Embodiment 4
Inhibiter is formed: mixed alkyl (4-vinyl)-benzyl-pyridine quaternary ammonium salt 50g, the nonionogenic tenside OP-10 of 1g
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
Embodiment 5
Inhibiter is formed: mixed alkyl dibromo ethylpyridine quaternary ammonium salt 50g, the nonionogenic tenside OP-10 of 1g
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
Comparative Examples 1
This Comparative Examples adopts host dimethylbenzene thiocarbamide, contrasts with embodiment 1.
Inhibiter is formed: dimethylbenzene thiocarbamide 50g, the nonionogenic tenside OP-10 of 1g
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
Comparative Examples 2
This Comparative Examples adopts host aldehyde ketone amine condenses Mannich base, contrasts with embodiment 1.
Inhibiter is formed: Mannich base 50g, the nonionogenic tenside OP-10 of 1g
Hydrochloric acid: 15%, 20%
Adopt above-mentioned inhibiter and hydrochloric acid to carry out the experiment of normal pressure static corrosion, with reference to the SY/T5405-1996 of China National Petroleum Corp.'s " acidifying inhibiter method for testing performance and evaluation index ", 60 ℃ of experimental temperatures, 90 ℃, etching time 4h the results are shown in down tabulation 1, table 2.
The table 1 of above-mentioned indication is:
The table 2 of above-mentioned indication is:
From table 1 and table 2 as can be seen, when other component was identical, mixed alkyl pyridine quaternary restrainer than dimethylbenzene thiocarbamide restrainer of the present invention containing, and aldehyde ketone amine condenses Mannich base restrainer corrosion inhibition rate will obviously improve a lot.
Embodiment 6
This example is a dynamic analog test.
Inhibiter is formed: mixed alkyl pyridine quaternary ammonium salt inhibiter 50g, the nonionogenic tenside OP-10 of 1g.
Experimental technique carries out with reference to the SY/T5405-1996 standard, HCl concentration 15%, inhibiter consumption 0.3%, 80 ℃ of corrosion temperatures, etching time 4h.
Experimental result: erosion rate 2.8g/m
2.h, corrosion inhibition rate 99.4%.
Claims (7)
1. a restrainer is characterized in that comprising following component, mixed alkyl pyridine quaternary ammonium salt 30～70%, and alcohol 25～50%, nonionogenic tenside 1～4%, surplus is a water, more than is weight percentage.
2. according to right 1 described restrainer, it is characterized in that: described mixed alkyl pyridine quaternary ammonium salt has following structure:
Wherein R is a substituting group, and R is Benzyl Chloride or propenyl chloride or epoxy chloropropane or p-chloromethyl styrene or ethylene dibromide, and wherein R ' is the C in ortho position or a position or the contraposition on the pyridine ring
1～C
3Alkyl.
3. restrainer according to claim 1 is characterized in that: described alcohol is methyl alcohol or ethanol or Virahol.
4. according to arbitrary described restrainer in the claim 1 to 3, it is characterized in that: described nonionogenic tenside is alkylphenol polyoxyethylene or peregal.
5. according to arbitrary described restrainer in the claim 1 to 3, it is characterized in that: described component is a mixed alkyl pyridine quaternary ammonium salt 40～60%, alcohol 35～55%, nonionogenic tenside 1～2%.
6. according to arbitrary described restrainer in the claim 1 to 3, it is characterized in that: the making method of described mixed alkyl pyridine quaternary ammonium salt is: mixed alkyl pyridine and quaternizing agent are according to molar ratio 1.1～2.5: 1, in the presence of 20-60% alcohol, control reaction temperature was reacted in 60-120 ℃ container backflow 4-16 hour, promptly obtained the mixed alkyl pyridine quaternary ammonium salt.
7. restrainer according to claim 6 is characterized in that: described alcohol is methyl alcohol or ethanol or Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110122663 CN102154654A (en) | 2011-05-10 | 2011-05-10 | Acid washing corrosion inhibitor |
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|---|---|---|---|
| CN 201110122663 CN102154654A (en) | 2011-05-10 | 2011-05-10 | Acid washing corrosion inhibitor |
Publications (1)
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|---|---|
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Family
ID=44436317
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289671A (en) * | 2013-05-28 | 2013-09-11 | 四川安东油气工程技术服务有限公司 | Corrosion inhibitor and preparation method thereof |
| CN104131303A (en) * | 2014-07-15 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Pickling corrosion inhibitor using industrial byproduct |
| CN104357860A (en) * | 2014-11-14 | 2015-02-18 | 三明学院 | Synthesis method of high-temperature-resistant acid pickling corrosion inhibitor |
| CN104726882A (en) * | 2015-03-26 | 2015-06-24 | 威海翔宇环保科技股份有限公司 | Efficient sulfuric acid pickling corrosion inhibitor and preparation method thereof |
| CN105568292A (en) * | 2016-01-05 | 2016-05-11 | 南京华洲新材料有限公司 | Alkyl pyridinium quaternary ammonium salt corrosion inhibitor used for inhibiting carbon dioxide corrosion and preparation method thereof |
| CN105568300A (en) * | 2016-01-05 | 2016-05-11 | 南京华洲新材料有限公司 | Pyridine quaternary ammonium salt corrosion inhibitor for industrial cleaning and preparing method of pyridine quaternary ammonium salt corrosion inhibitor |
| CN106011882A (en) * | 2016-07-12 | 2016-10-12 | 陕西省石油化工研究设计院 | Hydrofluoric acid corrosion inhibitor for power plant cleaning |
| CN106350056A (en) * | 2016-08-27 | 2017-01-25 | 中国石油集团渤海钻探工程有限公司 | Corrosion inhibitor applicable to crosslinked acid acidification at 120-140 DEG C and preparation method of corrosion inhibitor applicable to crosslinked acid acidification at 120-140 DEG C |
| CN106367057A (en) * | 2016-08-27 | 2017-02-01 | 中国石油集团渤海钻探工程有限公司 | Corrosion inhibitor used for acidizing and resisting to high temperature of 140-160 DEG C and preparation method for inhibitor |
| CN107418547A (en) * | 2017-08-29 | 2017-12-01 | 中国石油集团渤海钻探工程有限公司 | One kind is based on the high-temperature acidification corrosion inhibitor of tribenzyl (2 benzyl) pyridine ammonium chloride |
| CN107523287A (en) * | 2017-08-29 | 2017-12-29 | 中国石油集团渤海钻探工程有限公司 | A kind of combined high temperature acidification corrosion inhibitor based on pyridines quaternary ammonium salt |
| CN109776402A (en) * | 2019-01-30 | 2019-05-21 | 深圳市兆新能源股份有限公司 | Isopropylamine yl pyridines quaternary ammonium salt and preparation method thereof and aqueous cleaning aerosol |
| CN110105943A (en) * | 2019-06-04 | 2019-08-09 | 中海油常州涂料化工研究院有限公司 | A kind of high-temperature acidification corrosion inhibitor and preparation method thereof |
| CN111778511A (en) * | 2020-07-16 | 2020-10-16 | 太原工业学院 | Carbon steel corrosion inhibitor containing alkyl guanidine salt and preparation method and application thereof |
| CN111778509A (en) * | 2020-07-16 | 2020-10-16 | 太原工业学院 | Carbon steel corrosion inhibitor containing arginine derivative and preparation method and application thereof |
| CN113151836A (en) * | 2021-03-10 | 2021-07-23 | 武汉钢铁有限公司 | Corrosion inhibitor suitable for hot-rolled pickled steel, preparation method and application |
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| US5084210A (en) * | 1990-02-07 | 1992-01-28 | Chemlink Incorporated | Corrosion inhibitor |
| CN101343748A (en) * | 2007-07-13 | 2009-01-14 | 比亚迪股份有限公司 | Composition for electroplating acid washing and electroplating method using the composition |
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| US5084210A (en) * | 1990-02-07 | 1992-01-28 | Chemlink Incorporated | Corrosion inhibitor |
| CN101343748A (en) * | 2007-07-13 | 2009-01-14 | 比亚迪股份有限公司 | Composition for electroplating acid washing and electroplating method using the composition |
Non-Patent Citations (1)
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289671A (en) * | 2013-05-28 | 2013-09-11 | 四川安东油气工程技术服务有限公司 | Corrosion inhibitor and preparation method thereof |
| CN103289671B (en) * | 2013-05-28 | 2016-10-05 | 四川安东油气工程技术服务有限公司 | Corrosion inhibiter and preparation method thereof |
| CN104131303A (en) * | 2014-07-15 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Pickling corrosion inhibitor using industrial byproduct |
| CN104357860A (en) * | 2014-11-14 | 2015-02-18 | 三明学院 | Synthesis method of high-temperature-resistant acid pickling corrosion inhibitor |
| CN104726882A (en) * | 2015-03-26 | 2015-06-24 | 威海翔宇环保科技股份有限公司 | Efficient sulfuric acid pickling corrosion inhibitor and preparation method thereof |
| CN105568292A (en) * | 2016-01-05 | 2016-05-11 | 南京华洲新材料有限公司 | Alkyl pyridinium quaternary ammonium salt corrosion inhibitor used for inhibiting carbon dioxide corrosion and preparation method thereof |
| CN105568300A (en) * | 2016-01-05 | 2016-05-11 | 南京华洲新材料有限公司 | Pyridine quaternary ammonium salt corrosion inhibitor for industrial cleaning and preparing method of pyridine quaternary ammonium salt corrosion inhibitor |
| CN106011882A (en) * | 2016-07-12 | 2016-10-12 | 陕西省石油化工研究设计院 | Hydrofluoric acid corrosion inhibitor for power plant cleaning |
| CN106350056A (en) * | 2016-08-27 | 2017-01-25 | 中国石油集团渤海钻探工程有限公司 | Corrosion inhibitor applicable to crosslinked acid acidification at 120-140 DEG C and preparation method of corrosion inhibitor applicable to crosslinked acid acidification at 120-140 DEG C |
| CN106367057A (en) * | 2016-08-27 | 2017-02-01 | 中国石油集团渤海钻探工程有限公司 | Corrosion inhibitor used for acidizing and resisting to high temperature of 140-160 DEG C and preparation method for inhibitor |
| CN107418547A (en) * | 2017-08-29 | 2017-12-01 | 中国石油集团渤海钻探工程有限公司 | One kind is based on the high-temperature acidification corrosion inhibitor of tribenzyl (2 benzyl) pyridine ammonium chloride |
| CN107523287A (en) * | 2017-08-29 | 2017-12-29 | 中国石油集团渤海钻探工程有限公司 | A kind of combined high temperature acidification corrosion inhibitor based on pyridines quaternary ammonium salt |
| CN109776402A (en) * | 2019-01-30 | 2019-05-21 | 深圳市兆新能源股份有限公司 | Isopropylamine yl pyridines quaternary ammonium salt and preparation method thereof and aqueous cleaning aerosol |
| CN110105943A (en) * | 2019-06-04 | 2019-08-09 | 中海油常州涂料化工研究院有限公司 | A kind of high-temperature acidification corrosion inhibitor and preparation method thereof |
| CN111778511A (en) * | 2020-07-16 | 2020-10-16 | 太原工业学院 | Carbon steel corrosion inhibitor containing alkyl guanidine salt and preparation method and application thereof |
| CN111778509A (en) * | 2020-07-16 | 2020-10-16 | 太原工业学院 | Carbon steel corrosion inhibitor containing arginine derivative and preparation method and application thereof |
| CN111778511B (en) * | 2020-07-16 | 2023-02-07 | 太原工业学院 | Carbon steel corrosion inhibitor containing alkyl guanidine salt and preparation method and application thereof |
| CN113151836A (en) * | 2021-03-10 | 2021-07-23 | 武汉钢铁有限公司 | Corrosion inhibitor suitable for hot-rolled pickled steel, preparation method and application |
| CN113151836B (en) * | 2021-03-10 | 2022-12-23 | 武汉钢铁有限公司 | Corrosion inhibitor suitable for hot-rolled pickled steel, preparation method and application |
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Application publication date: 20110817 |