CN1047409C - Normal-temp copper pickling corrosion inhibitor - Google Patents
Normal-temp copper pickling corrosion inhibitor Download PDFInfo
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- CN1047409C CN1047409C CN97105718A CN97105718A CN1047409C CN 1047409 C CN1047409 C CN 1047409C CN 97105718 A CN97105718 A CN 97105718A CN 97105718 A CN97105718 A CN 97105718A CN 1047409 C CN1047409 C CN 1047409C
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- ammonium chloride
- dodecyl
- thiocarbamide
- copper
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Abstract
The present invention relates to a normal-temperature copper pickling corrosion inhibitor applicable to the mediums of hydrochloric acid, and is composed of thiazoles, organic amine, surface active agents, ethanol, water, coloring agent, thiurea and derivatives, etc. The present invention is characterized in that several kinds of organic matters are synthesized into compounds containing pi-bonds, benzene rings and long bond groups under certain reaction conditions. Since the compounds contain the polar groups of N, S and O with higher electronegativity, physical and chemical adsorption are carried out on the surfaces of metals so that the double electric layer structure of the interface of metal/solution is changed, and activation energy in the ionizing process of the metals is enhanced. Therefore, the present invention has the advantages of greatly improved adsorption capacity on the surface of copper and favorable protective effect of carbon steel.
Description
The invention belongs to chemical treatment method field, metallic surface, specifically a kind of pipeline scale removal that is used for fields such as electric power, heating power and chemical industry, have the hydrochloric acid medium normal-temp copper pickling corrosion inhibitor of efficient corrosion inhibition.
Copper and copper alloy be main material as heat exchanger in power-equipment, though temperature that they bear and pressure are not high, because wall thickness only is 1 millimeter, so require its corrosion speed lower; Condenser (water cooler) and heat exchanger tube mainly use brass.Conventional condenser, by recirculated cooling water, water coolant can be fresh water, natural water, salt water or seawater in the pipe, the pipe outside is steam discharge and condensed water, volumetric shrinkage when condensing owing to steam discharge, the steam of condenser then is vacuum state.In case improper because of pickling, brazed copper tube corrodes (dezincify) when leaking, water coolant will leak in condensed water, cause condensed water and boiler contamination, but also can cause accidents such as the burn into fouling of boiler unit and salification.Because water coolant not soften processings, it easily generates carbonate deposit in condenser copper tubes, and this incrustation scale is met the hydrochloric acid plate and easily dissolved, and need not to heat, but in pickling descaling, sourly also can cause in various degree corrosion failure to base metal.So, in acid solution, to add the possibility that a kind of corrosion speed that can guarantee the base metal material reduces and hydrogen embrittlement takes place be suppressed at below the security level, also do not influence simultaneously the material of sour dissolution rate to dirt-→ restrainer.
At present, widely used acidic medium copper inhibitor, most organic substances that adopt with absorption and complexing action, be the compound that contains elements such as N, S, O, P mostly, as compounds such as amine, aldoketones, thiourea derivative, heterocyclic compound, pyridine derivate, quaternary amines, they all contain solely to electronics can with metal generation chemisorption such as Fe, Cu, Ni.Contain the compound of two keys, three key, phenyl ring,, can utilize their towering-electronics to carry out chemisorption as propiolic alcohol, benzene nitrile etc.Though it is they all have certain corrosion mitigating effect, also not satisfactory.For example 1, thiocarbamide and derivative thereof: the Thiourea inhibiter easily becomes the chocolate film in the copper surface adsorption, also easily dirty thing is wrapped in wherein simultaneously, influences dissolved dirt speed and effect; Thiourea derivative such as di-o-tolyl-thiourea, poorly water-soluble, easily caking earlier with warm water softening water furnishing pasty state, is poured in the acid and is stirred, and have certain toxicity during use.
2, aldehyde-amine polycondensate class: be to be raw material, in acidic medium, be polymerized with formaldehyde and aniline.Though it is simple to have synthesis technique, good water solubility has certain toxicity, and human body is had harm, also has unstable properties (changing with polymerizing condition difference, shelf-time difference) simultaneously.
3, pyridine and derivatives class thereof: its raw material is to separate in the byproduct that obtains from the female oily refining process of coal tar page or leaf, and peculiar stink has limited its application.
4, some utilize the inhibiter of chemical by-product processing: its composition is comparatively complicated, mostly be the macromolecular compound that contains S, N, mostly do not pass through strict fractionation, useful component and useless component are all therein, so the consumption height is arranged, water-soluble and the solubility in acid that has is not so good, also has certain taste, therefore is difficult to obtain the better byproduct inhibiter of performance.
5, MBT (2-mercaptobenzothiazole): copper alloy is had good corrosion inhibiting ability, but its solubility property in pickling is relatively poor, using dosage is restricted.
The object of the present invention is to provide a kind of normal-temp copper pickling corrosion inhibitor that can produce physics and chemisorption and raising metal surface corrosion inhibition performance simultaneously.
The object of the present invention is achieved like this: it is made up of following component and ratio of weight and number:
Thiazoles 5-16, organic amine 6-15, tensio-active agent 7-15
Industrial alcohol 50-75, water 3-10, tinting material 0.05-0.5,
Thiocarbamide and derivative 0.0-5.0.
Its preparation method is: thiazoles, organic amine, tensio-active agent, industrial alcohol, water and thiocarbamide and derivative are pressed above-mentioned ratio of weight and number, together join heating and stirring in the reactor, back flow reaction 1-2.5 hour, the cooling back adds desired tinting material and is finished product, and its proportion is 0.82-0.89 (20 ℃).Above-mentioned back flow reaction temperature is controlled between 70-75 ℃.Inhibiter of the present invention also can be united use with other pure molten synergistic agent such as N, S compound that contain.
Thiazoles of the present invention is meant 2-sulfydryl benzo thiophene (MBT) and benzothiazyl disulfide (MBTS).
Organic amine of the present invention is meant hexamethylenetetramine, 4-butyl amine and tribenzyl methylamine.
Tensio-active agent of the present invention is meant alkylphenol polyoxyethylene (TX-10), fatty alcohol-polyoxyethylene ether (peregal), alkylphenol polyoxyethylene (OP), dodecyl benzyl dimethyl ammonium chloride (1227), dodecyl dimethyl benzyl ammonium bromide (bromogeramine), Dodecyl trimethyl ammonium chloride (1231), cetyl trimethylammonium bromide (1631), octadecyl trimethyl ammonium chloride (1831).
Thiocarbamide of the present invention and derivative are meant thiocarbamide, diphenyl thiourea and di-o-tolyl-thiourea.
Tinting material of the present invention is meant 5NB, reaches alkalescence or acid developer.
The present invention synthesizes several organic substances the compound that contains towering key, phenyl ring, long key group under the certain reaction condition.Owing to contain N, S, polar group that the O electronegativity is bigger in the compound, carry out physics and chemisorption in the metallic surface, changed the structure of the electrostatic double layer of metal/solution interface, improved the activation energy of metal ion process.Thereby improved its adsorptive power widely on the copper surface, and demonstrating good corrosion inhibition, it also has good protection effect to carbon steel simultaneously.
Below will the invention will be further described by embodiment: example 1:
5 gram MBT and six (Asia) methyl tetramines of 8 grams, 11 gram dodecyl benzyl dimethyl ammonium chlorides, 0.5 gram fatty alcohol-polyoxyethylene ether, 0.1 gram thiocarbamide, 70 gram ethanol and 5.4 gram water are together put into to have stir and the reaction flask of reflux, back flow reaction 1 hour, the back flow reaction temperature is controlled between 70-75 ℃.Example 2:
12 gram MBT and six (Asia) methyl tetramines of 7 grams, 8 gram dodecyl benzyl dimethyl ammonium chlorides, 0.5 gram fatty alcohol-polyoxyethylene ether, 1 gram diphenyl thiourea, 65 gram ethanol and 6.5 gram water are together put into to have stir and the reaction flask of reflux, back flow reaction 1.5 hours, the back flow reaction temperature is controlled between 70-75 ℃.Example 3
With 16 gram MBT and six (Asia) methyl tetramines of 12 grams, 7 gram dodecyl benzyl dimethyl ammonium chlorides, 0.4 gram fatty alcohol-polyoxyethylene ether, 1 gram di-o-tolyl-thiourea, 59.6 gram ethanol and 5 gram water, method is the same, back flow reaction 2.5 hours.Test conditions:
1. medium: 6%HCl; 2. molten amount: 400 milliliters;
3. ferric ion＞500 mg/litre; 4. hardness ions＞1000 mg/litre;
5. temperature: normal temperature; 6. state: stirred solution; 7. pressure: normal pressure; 8. time: 4 hours.Test-results:
Density of corrosion inhibitor corrosion speed (g/m
2H) brass inhibition
(%) brass red copper carbon steel 20 efficient (%)
Example 1 0.4 0.0382 0.0872 0.7966 97.06
Example 2 0.4 0.010 0.4506 0.5763 99.23
Example 3 0.4 0.005 0.3343 0.5254 99.62
The blank corrosion speed of [notes] brass is 1.2977g/m
2.h.
Claims (2)
1, a kind of normal-temp copper pickling corrosion inhibitor that is applicable in the hydrochloric acid medium, it is made up of following component and ratio of weight and number:
2-mercaptobenzothiazole 5-16, hexamethylenetetramine 6-15,
Alkylphenol polyoxyethylene tensio-active agent 7-15, industrial alcohol 50-75,
Water 3-10,5NB tinting material 0.05-0.5, thiocarbamide 0.0-5.0.Above-mentioned thiazole also can be a benzothiazyl disulfide; Above-mentioned hexamethylenetetramine also can be 4-butyl amine or tribenzyl methylamine; Thiocarbamide also can be diphenyl thiourea or di-o-tolyl-thiourea; Tensio-active agent also can be selected fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride for use; Above-mentioned tinting material also can be alkalescence or acid developer.
2, a kind of preparation method of claim 1 copper pickling corrosion inhibitor, it is characterized in that 2-mercaptobenzothiazole, hexamethylenetetramine, alkylphenol polyoxyethylene tensio-active agent, industrial alcohol, water and thiocarbamide by above-mentioned ratio of weight and number, together join heating and stirring in the reactor, back flow reaction 1-2.5 hour, reflux temperature is at 70-75 ℃, and the cooling back adds an amount of 5NB tinting material and is finished product; Above-mentioned thiazole also can be a benzothiazyl disulfide; Above-mentioned hexamethylenetetramine also can be 4-butyl amine or tribenzyl methylamine; Thiocarbamide also can be diphenyl thiourea or di-o-tolyl-thiourea; Tensio-active agent also can be selected fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride for use; Above-mentioned tinting material also can be alkalescence or acid developer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105718A CN1047409C (en) | 1997-03-07 | 1997-03-07 | Normal-temp copper pickling corrosion inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105718A CN1047409C (en) | 1997-03-07 | 1997-03-07 | Normal-temp copper pickling corrosion inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166538A CN1166538A (en) | 1997-12-03 |
| CN1047409C true CN1047409C (en) | 1999-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97105718A Expired - Fee Related CN1047409C (en) | 1997-03-07 | 1997-03-07 | Normal-temp copper pickling corrosion inhibitor |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091173C (en) * | 1999-09-01 | 2002-09-18 | 中国科学院金属研究所 | Protecting agent able to remove rust from surface of copper or copper alloy |
| CN101892489B (en) * | 2010-07-23 | 2012-11-07 | 广州唯普电力科技有限公司 | Cleaning agent for flue dust scale on surface of gas heat exchanger of gas desulfurization system and preparation method thereof |
| CN104047012A (en) * | 2014-06-23 | 2014-09-17 | 梧州恒声电子科技有限公司 | Metal oil removal agent and preparation method thereof |
| CN104047003A (en) * | 2014-06-23 | 2014-09-17 | 梧州恒声电子科技有限公司 | Method for removing oxide scale on surface of copper |
| CN104047005A (en) * | 2014-06-23 | 2014-09-17 | 梧州恒声电子科技有限公司 | Method for removing oil of copper and copper alloy |
| 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 |
| CN104404548B (en) * | 2014-11-14 | 2017-08-11 | 山东中实易通集团有限公司 | A kind of Chemical cleaning molecular self-assembled monolayer corrosion inhibiter and preparation method thereof |
| CN104762581A (en) * | 2015-03-23 | 2015-07-08 | 成都振中电气有限公司 | Anticorrosion processing method used for surface of metal member |
| CN104762580A (en) * | 2015-03-23 | 2015-07-08 | 成都振中电气有限公司 | Galvanizing technology good for uniformity of galvanizing layer thickness |
| CN105327908A (en) * | 2015-11-09 | 2016-02-17 | 云南钛业股份有限公司 | Method for removing incrustation on inner wall of copper pipe of diffusion pump |
| CN108179426A (en) * | 2018-03-05 | 2018-06-19 | 苏州科技大学 | A kind of copper and its alloy pickling corrosion inhibiter and preparation method thereof |
| CN111218687B (en) * | 2020-03-30 | 2022-01-21 | 惠州宇盛机械设备有限公司 | Chemical polishing solution for precise copper alloy workpiece |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104012A2 (en) * | 1982-09-21 | 1984-03-28 | Halliburton Company | Composition and method for simultaneously removing iron and copper scales from ferrous metal surfaces |
| JPS59208082A (en) * | 1983-05-11 | 1984-11-26 | Tatsuta Electric Wire & Cable Co Ltd | Corrosion preventive method of metal of cooling water system |
-
1997
- 1997-03-07 CN CN97105718A patent/CN1047409C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104012A2 (en) * | 1982-09-21 | 1984-03-28 | Halliburton Company | Composition and method for simultaneously removing iron and copper scales from ferrous metal surfaces |
| JPS59208082A (en) * | 1983-05-11 | 1984-11-26 | Tatsuta Electric Wire & Cable Co Ltd | Corrosion preventive method of metal of cooling water system |
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| CN1166538A (en) | 1997-12-03 |
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