CN1092250C - Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution - Google Patents
Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution Download PDFInfo
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- CN1092250C CN1092250C CN98104900A CN98104900A CN1092250C CN 1092250 C CN1092250 C CN 1092250C CN 98104900 A CN98104900 A CN 98104900A CN 98104900 A CN98104900 A CN 98104900A CN 1092250 C CN1092250 C CN 1092250C
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- corrosion inhibitor
- corrosion
- steel
- triethanolamine
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- 238000005260 corrosion Methods 0.000 title claims abstract description 69
- 230000007797 corrosion Effects 0.000 title claims abstract description 68
- 239000003112 inhibitor Substances 0.000 title claims abstract description 41
- 239000010959 steel Substances 0.000 title claims abstract description 40
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 38
- 239000012266 salt solution Substances 0.000 title claims abstract description 11
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 17
- 229910052742 iron Inorganic materials 0.000 title claims description 8
- 244000101724 Apium graveolens Dulce Group Species 0.000 title 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 title 1
- 235000010591 Appio Nutrition 0.000 title 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims abstract 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 6
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 18
- 230000005764 inhibitory process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
一种抑制钢铁在10%～25%食盐溶液中腐蚀的新型缓蚀剂，是由41%～61%的硫脲、0.5%～3.5%的磷酸三乙醇胺、0.5%～3.5%的磷酸二氢锌和35%～55%的乌洛托品所组成。当浓度为1000ppm～2500ppm时，这种缓蚀剂不仅能在钢铁表面形成多重保护膜，而且当膜破损时尚具有自修复的能力，因此，对抑制钢铁腐蚀尤其有效，对A3钢的缓蚀率高达98%。其主要特点是：(1)高效。(2)剂量小，成本低。(3)无毒，无公害。(4)工序简单，不必预膜。A new type of corrosion inhibitor that inhibits the corrosion of steel in 10% to 25% salt solution is composed of 41% to 61% thiourea, 0.5% to 3.5% triethanolamine phosphate, and 0.5% to 3.5% dihydrogen phosphate Composed of zinc and 35% to 55% urotropine. When the concentration is 1000ppm-2500ppm, this corrosion inhibitor can not only form multiple protective films on the steel surface, but also has the ability of self-repair when the film is damaged. Therefore, it is especially effective for inhibiting the corrosion of steel. The rate is as high as 98%. Its main features are: (1) High efficiency. (2) The dosage is small and the cost is low. (3) Non-toxic and pollution-free. (4) The process is simple and no pre-filming is necessary.
Description
The invention relates to the field of chemistry, in particular to a novel corrosion inhibitor (XM-505 for short) for inhibiting corrosion of steel in 10-25% salt solution and a preparation and use method thereof.
Common salt solution of 10-25% is used as secondary refrigerant in refrigeration industry. Although corrosion inhibitors have been used for over 100 years, there has been little research on corrosion inhibitors that inhibit corrosion of steel in 10% to 25% salt solutions. Studies by Boehringer et al indicate that 4000ppm potassium dichromate, 300ppm mpA, 10ppm HpMA and Zn are added to 10-15% NaCl brine++20ppm (total concentration 4330ppm) can lead the corrosion inhibition rate of the carbon steel to reach 95% [ total corrosion control]1995, 9 (1): pages 32-33]. The potassium dichromate formula is effective, but has serious problems: first, potassium dichromate is a dangerous anode type corrosion inhibitor, if the adding amount is insufficient, not only can steel be passivated to play a role in protection, but also the corrosion of the steel can be accelerated, so the required dosage is large. Secondly, potassium dichromate is an extremely toxic carcinogen and can pollute the environment on which humans rely for survival. Thirdly, the corrosion inhibition rate is to be further improved.
Aiming at the problems of the potassium dichromate formula, the invention aims to develop a novel corrosion inhibitor which has higher corrosion inhibition rate, smaller dosage and no toxicity, so as to replace the extremely toxic potassium dichromate formula.
In order to realize the purpose of the invention, the technical route and the action principle are as follows: (1) thiourea is selected as the main component of the novel corrosion inhibitor. Since the thiourea has two hybridized atoms of N and S in the molecule, it can react with Fe++Complexing and finally converting into insoluble iron sulfide protective film. (2) The triethanolamine phosphate synthesized by the molecular cutting method further enhances the synergistic effect between the alcohol amine group and the phosphate radical. It dissolves O in2Under the synergistic effect of the components, triethanolamine phosphate and gamma-Fe can be formed on the surface of steel2O3、Fe3O4And FePO4The formed multiple protective films(ii) a Meanwhile, the film has a plurality of branched chains, and has self-repairing capability when the film is damaged. (3) Zinc dihydrogen phosphate is first introduced into the formulation of such corrosion inhibitors. It is mixed with sodium dihydrogen phosphate or non-hydrolyzable zinc salt (such as ZnSO)4Etc.) have more advantages than others. The zinc dihydrogen phosphate has hydrolyzability and can form insoluble Zn at the cathode reaction position of the steel surface3(PO4)2Deposited film (zinc phosphating of steel) which is sodium dihydrogen phosphate or non-hydrolyzable zinc salt (such as ZnSO)4Etc.) are not available. Zinc dihydrogen phosphate can be ionized, and phosphate radical can dissolve O2Under the synergistic effect of (A) with Fe++Reaction to form insoluble FePO on the surface of steel4Deposited film (iron and steel based phosphating) with the same effect as with sodium dihydrogen phosphate, Zn++Possibly with Zn (OH)2Forma cathode-type deposit film on the surface of steel, which is weak but has an effect of increasing efficiencyWith or without the use of non-hydrolysable zinc salts (e.g. ZnSO)4Etc.) are the same. (4) Urotropin is introduced into the novel corrosion inhibitor. As the molecule of the urotropine has four hybrid atoms N, the urotropine can be complexed with iron atoms exposed on the surface of steel and directly adsorbed on the surface of the steel, so that the process of corrosion of the steel and the iron in a negative and positive conjugation process is inhibited, the corrosion inhibitor is prevented from being dissolved too fast in iron on an anode during the formation of a protective film on the surface of the steel and the iron so that the corrosion rate of the steel and the iron is increased, and meanwhile, the urotropine can also be used as an effective component of the protective film. (5) By a compound test, the optimized combination is achieved, and the corrosion inhibition effect is further improved. Experiments show that: the four components of thiourea, triethanolamine phosphate, zinc dihydrogen phosphate and urotropine are perfectly matched as a whole (XM-505) for the first time, have obvious synergistic effect and are particularly effective in inhibiting the corrosion of steel in 10-25% salt solution.
The method for inhibiting the corrosion of steel in 10-25% salt solution includes adding 1000-2500 ppm XM-505 salt water medium corrosion inhibitor into the salt solution and its preparation and application.
The XM-505 brine medium corrosion inhibitor consists of 41 to 61 percent of thiourea, 0.5 to 3.5 percent of triethanolamine phosphate, 0.5 to 3.5 percent of zinc dihydrogen phosphate and 35 to 55 percent of urotropine. The components of the corrosion inhibitor are preferably used in the form of solutions.
Preparing a corrosion inhibitor: (1) the mixture of thiourea and urotropine is prepared into an aqueous solution, namely solution A, the total content is 100mg/ml, and the ratio of thiourea to urotropine is 51: 45 (weight ratio). (2) Preparing mixed liquor B with the total content of 100mg/ml according to the weight ratio of the triethanolamine phosphate to the zinc dihydrogen phosphate of 1: 1. When in preparation, the following reaction formula is firstly adopted, namely
The dosage of the solution A and the dosage of the solution B are calculated according to the weight of the salt solution, the required concentration of the corrosion inhibitor and the component proportion of the corrosion inhibitor. Adding the solution A into the salt solution, stirring, adding the solution B, and stirring.
When the concentration of the XM-505 corrosion inhibitor for the saline medium is 2000ppm, the weight loss method is used for measuring the corrosion inhibitor to A3The corrosion inhibition rate of the steel is as high as 98%, and the steel sample has good appearance and brightness as before after 1800-hour weight loss test. Compared with the potassium dichromate formula developed by Bos et al, the corrosion inhibition rate is higher by 3%, while the dosage is only 46.2% of the latter, and the raw materials are nontoxic and pollution-free. It can be seen that XM-505 is in saline solutionThe comprehensive performance of the corrosion inhibitor is far better than that of a potassium dichromate formula, and the corrosion inhibitor is used for replacing an extremely toxic potassium dichromate formula, so that not only can greater economic benefit be obtained, but also the environment depending on the existence of human can be protected.
The XM-505 brine medium corrosion inhibitor is mainly characterized in that: (1) high efficiency. (2) Low dosage and low cost. (3) No toxicity and no public nuisance. (4) The process is simple and no pre-film is needed.
Example 1: the test solution is 22.4 without corrosion inhibitor% of common salt solution and 22.4% of common salt solution added with 2000ppm of XM-505 saline medium corrosion inhibitor consisting of 51% of thiourea, 2% of triethanolamine phosphate, 2% of zinc dihydrogen phosphate and 45% of urotropine (weight percentage). Test Material A3Steel with a sample size of 5X 2.5X 0.2cm and a surface area of 28cm2. All the samples are polished step by metallographic abrasive paper, then washed by tap water and absolute alcohol, dried by cold air, and placed in a dryer for more than 24 hours for later use.
The experiment was performed using a weight loss method. Weighing a sample, soaking the sample in a test solution for 1800 hours (at room temperature and in a static state), treating the taken sample according to a GB6384-86 method, weighing, and calculating the corrosion rate upsilon of a steel sample according to the following formula (3), namely
υ(mm/y)＝8.76×104X Δ w/s × t × ρ. (3) in the formula: Δ w is the weight loss (g) of the steel sample, S is the surface area (cm) of the steel sample2) T is the soaking time (h), and rho is the steel density (g/cm)3)。
Then calculating the corrosion inhibition rate E of the corrosion inhibitor on the steel according to the following formula (4), namely
E(％)＝(υo-υc)/υoX 100. (4) wherein: upsilon isoCorrosion rate upsilon of steel sample without corrosion inhibitorcThe steel-like corrosion rate for a given corrosion inhibitor.
The test results were as follows: when the concentration of the corrosion inhibitor is 2000ppm, for A3The corrosion inhibition rate of the steel is as high as 98%, and the appearance of the steel sample is good and bright as before.
Example 2: the process and the corrosion inhibitor composition are as in example 1, for A, when the concentration of the corrosion inhibitor is 2500ppm3The corrosion inhibition rate of the steel is as high as 97.7%, and the appearance of the steel sample is good and bright as before.
Example 3: the process and the corrosion inhibitor composition are as in example 1, for A, when the concentration of the corrosion inhibitor is 1000ppm3The corrosion inhibition rate of the steel reaches 95.6%, and the steel sample has good appearance and brightness as before.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98104900A CN1092250C (en) | 1998-04-08 | 1998-04-08 | Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98104900A CN1092250C (en) | 1998-04-08 | 1998-04-08 | Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231347A CN1231347A (en) | 1999-10-13 |
| CN1092250C true CN1092250C (en) | 2002-10-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98104900A Expired - Fee Related CN1092250C (en) | 1998-04-08 | 1998-04-08 | Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1092250C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457974C (en) * | 2006-01-19 | 2009-02-04 | 重庆大学 | Metal pickling inhibitor and method for preparing the same |
| CN102953067B (en) | 2011-08-19 | 2014-11-26 | 中国石油天然气股份有限公司 | Mannich base decalcification corrosion inhibitor and its preparation and application |
| CN106590321B (en) * | 2015-10-19 | 2019-07-02 | 中国科学院海洋研究所 | A kind of glass fiber corrosion inhibitor self-healing coating and preparation method |
| CN106433465B (en) * | 2016-09-13 | 2020-05-01 | 张滨 | Electronic protective agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932303A (en) * | 1973-06-04 | 1976-01-13 | Calgon Corporation | Corrosion inhibition with triethanolamine phosphate ester compositions |
| US4409121A (en) * | 1980-07-21 | 1983-10-11 | Uop Inc. | Corrosion inhibitors |
| KR910007126A (en) * | 1989-09-01 | 1991-04-30 | 경상현 | Method of forming buried resistive contact |
| EP0541318A1 (en) * | 1991-11-06 | 1993-05-12 | Diversey Corporation | Cooling water treatment composition and method |
| CN1087372A (en) * | 1992-11-27 | 1994-06-01 | 郭湘泗 | The manufacture method of deicing fluid |
| CN1097462A (en) * | 1993-07-12 | 1995-01-18 | 王国辉 | Powerful water-base cutting fluid |
-
1998
- 1998-04-08 CN CN98104900A patent/CN1092250C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932303A (en) * | 1973-06-04 | 1976-01-13 | Calgon Corporation | Corrosion inhibition with triethanolamine phosphate ester compositions |
| US4409121A (en) * | 1980-07-21 | 1983-10-11 | Uop Inc. | Corrosion inhibitors |
| KR910007126A (en) * | 1989-09-01 | 1991-04-30 | 경상현 | Method of forming buried resistive contact |
| EP0541318A1 (en) * | 1991-11-06 | 1993-05-12 | Diversey Corporation | Cooling water treatment composition and method |
| CN1087372A (en) * | 1992-11-27 | 1994-06-01 | 郭湘泗 | The manufacture method of deicing fluid |
| CN1097462A (en) * | 1993-07-12 | 1995-01-18 | 王国辉 | Powerful water-base cutting fluid |
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| Publication number | Publication date |
|---|---|
| CN1231347A (en) | 1999-10-13 |
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