CN112795927A - Hydrochloric acid pickling corrosion-inhibition fog inhibitor and preparation method thereof - Google Patents
Hydrochloric acid pickling corrosion-inhibition fog inhibitor and preparation method thereof Download PDFInfo
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- CN112795927A CN112795927A CN202011579022.XA CN202011579022A CN112795927A CN 112795927 A CN112795927 A CN 112795927A CN 202011579022 A CN202011579022 A CN 202011579022A CN 112795927 A CN112795927 A CN 112795927A
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- acid
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/063—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors heterocyclic compounds
Abstract
The invention discloses a hydrochloric acid pickling corrosion inhibition fog inhibitor, wherein each hundred parts of the corrosion inhibition fog inhibitor comprise 5-25 parts of polyaspartic acid, 5-25 parts of amino acid, 1-5 parts of alkyl glycoside surfactant and the balance of water; the total mass of the polyaspartic acid and the amino acid is not less than 20 parts; the polyaspartic acid is obtained by thermal polycondensation of L-aspartic acid at 160 +/-5 ℃ for 1-3 h under the action of a catalyst phosphoric acid and hydrolysis of ammonia water; controlling the pH value to be 10.5-11.0 in the ammonia water hydrolysis process; the amino acid is at least one of lysine, arginine and histidine. The corrosion-inhibition fog inhibitor is prepared by qualitatively preparing polyaspartic acid, selecting the alkyl glycoside surfactant suitable for the polyaspartic acid, and combining amino acid, so that the three raw materials generate mutual synergy, stable and excellent corrosion-inhibition and fog-inhibition effects can be obtained, the defects of the raw materials can be avoided, the disadvantage that the conventional environment-friendly product is poor in performance is overcome, and the corrosion-inhibition fog inhibitor has obvious practical value.
Description
Technical Field
The invention relates to the technical field of acid-washing fog inhibitors, in particular to a hydrochloric acid-washing corrosion-inhibition fog inhibitor and a preparation method thereof.
Background
The use of acid solution to remove scale and rust from metal surfaces is one method of cleaning metal surfaces, known as pickling. The use of strong acid to clean metal surfaces is an important means for surface pretreatment and descaling of pipelines and boiler systems, and is widely applied to industries such as metal materials, machinery, metallurgy, chemical engineering and the like. In the strong acid cleaning, hydrochloric acid is the most widely used pickling agent, and has the advantages of large pickling capacity, high speed, no hydrogen embrittlement and the like, but the hydrochloric acid has strong corrosivity to metal, the phenomenon of over-etching often occurs, and the hydrochloric acid is volatile, so that acid mist on a pickling site is diffused, and serious environmental pollution and harm to human bodies are caused.
In order to solve the problems of acid mist and corrosion in the acid pickling process, people usually add a corrosion-inhibiting fog inhibitor into the acid liquor as an auxiliary agent which has a synergistic effect with the acid liquor and reduces pollution. However, most of the components of the existing fog inhibitor are not environment-friendly enough, for example, the common raw materials of the acid-washing fog inhibitor comprise amines, imidazolines, polyether surfactants, thiourea and the like, some of the substances have toxicity and are difficult to degrade, and the large amount of the substances can increase the pollution and the treatment pressure to the environment and waste water. In response to the environmental protection requirement, people propose to prepare the corrosion-inhibiting fog inhibitor by polyaspartic acid and surfactant dodecyl phenol polyoxyethylene ether. The polyaspartic acid is a biodegradable polymer substance with a corrosion inhibition effect, but the polyaspartic acid purchased in the market has the situation that the corrosion inhibition effect is not ideal, the fog inhibition effect of the polyaspartic acid is low, and the dodecyl polyoxyethylene ether for exerting the fog inhibition effect has no biodegradability, so that the existing corrosion and fog inhibition agent is difficult to achieve the excellent corrosion inhibition, fog inhibition and environmental protection.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the hydrochloric acid pickling corrosion and fog inhibition agent which has obvious corrosion inhibition and fog inhibition effects and is stable, and the corrosion and fog inhibition agent uses all biodegradable environment-friendly raw material components, thereby ensuring the use performance and having real environment friendliness.
In order to achieve the purpose, the invention provides a hydrochloric acid pickling corrosion and fog inhibitor, wherein each hundred parts of the corrosion and fog inhibitor comprise the following components in parts by mass:
5-25 parts of polyaspartic acid, 5-25 parts of amino acid, 1-5 parts of alkyl glycoside surfactant and the balance of water; the total mass of the polyaspartic acid and the amino acid is not less than 20 parts;
the polyaspartic acid is obtained by thermal polycondensation of L-aspartic acid at 160 +/-5 ℃ for 1-3 h under the action of catalyst phosphoric acid and hydrolysis by ammonia water, wherein the pH value of the hydrolysis process of the ammonia water is controlled to be 10.5-11.0;
the amino acid is at least one of lysine, arginine and histidine.
The hydrochloric acid pickling corrosion-inhibition fog-inhibition agent disclosed by the invention is prepared by compounding polyaspartic acid obtained under specific preparation conditions with an alkyl glycoside surfactant instead of polyaspartic acid with a general molecular weight of 5000-8000 in the market as a raw material, and simultaneously, a synergistic mechanism of the two components in the aspect of corrosion-inhibition and fog-inhibition effects is regulated by selecting specific amino acid molecules, so that stable and excellent corrosion-inhibition and fog-inhibition using effects are realized. The stable complex property of the polyaspartic acid is directionally obtained by controlling the polymerization temperature and the polymerization time of the polyaspartic acid, further limiting ammonia water as a hydrolysate and controlling the pH environment in the hydrolysis process, and on the basis, one or more of three specific amino acids of lysine, arginine and histidine are combined, so that the corrosion inhibition effect can be remarkably improved, and the foam fog inhibition effect of the alkyl glycoside surfactant can be synergistically promoted. In addition, all the selected components are biodegradable raw materials, so that the usability and the environmental friendliness are really achieved, and the biodegradable plastic has obvious market application value.
As a limitation to the technical scheme, the polyaspartic acid has an average molecular weight of 1000-3000.
As a limitation to the technical scheme, the alkyl glycoside surfactant is APG0810 or/and APG 0814.
As a limitation to the technical scheme, the usage amount of the corrosion and fog inhibitor is 0.1-0.5%.
The average molecular weight of the components of the polyaspartic acid and the preferable raw materials of the amino acid and the alkyl glycoside surfactant are further limited, so that the corrosion-inhibition fog inhibitor obtained by compounding is more stable and has better service performance. Meanwhile, the corrosion and fog inhibitor can meet the use requirement on the premise of less dosage.
Meanwhile, the invention also provides a preparation method of the hydrochloric acid pickling corrosion-inhibition fog inhibitor, which comprises the following steps:
a-1, adding L-aspartic acid into a polymerization reaction kettle, then adding a catalyst phosphoric acid, fully and uniformly stirring, heating for polymerization under a continuous stirring state, controlling the polymerization temperature to be 160 +/-5 ℃ and the polymerization time to be 1-3 h;
a-2, after the polymerization reaction is finished and the reaction materials are cooled to room temperature, adding ammonia water into the reaction materials for hydrolysis reaction, controlling the pH value in the hydrolysis process to be 10.5-11.0, after the materials are completely dissolved, keeping the temperature to be 50-60 ℃, continuously stirring for 1-2 hours, and finishing the reaction to obtain a product, namely polyaspartic acid;
b. and (b) mixing the polyaspartic acid with the average molecular weight of 1000-3000, which is prepared in the step a-2, with an alkyl glycoside surfactant, adding amino acid, and fully and uniformly stirring to obtain a light yellow to reddish brown transparent solution, namely the hydrochloric acid pickling corrosion inhibition fog inhibitor.
The corrosion-inhibition fog inhibitor is prepared by firstly preparing polyaspartic acid raw material, and obtaining polyaspartic acid which has specific molecular structure and performance and is suitable for subsequent compounding under specific polymerization temperature, polymerization time and hydrolysis conditions; and then, the polyaspartic acid is sequentially mixed with the alkyl glycoside surfactant and the amino acid, so that a better synergistic effect is generated among the compound components, and the stable using effect of the corrosion and fog inhibitor is ensured.
As a limitation to the technical scheme, the adding amount of the catalyst phosphoric acid in the step a-1 accounts for 1-2.5% of the mass of the L-aspartic acid.
As a limitation on the technical scheme, the mass fraction of the ammonia water in the step a-2 is 20%, the adding amount of the ammonia water is 65-75% of the mass of the L-aspartic acid, and the ammonia water is controlled to be added at a constant speed within 1-2 h.
Further limiting the dosage of the catalyst used in the polymerization reaction of the polyaspartic acid, the dosage of the ammonia water in the hydrolysis reaction and the flow acceleration, and stably controlling the average molecular weight, the molecular structure and the performance of the polyaspartic acid.
In conclusion, the hydrochloric acid pickling corrosion and fog inhibitor of the invention uses all biodegradable raw material components, ensures the environmental protection of the corrosion and fog inhibitor, simultaneously, qualitatively prepares the polyaspartic acid in function, selects the alkyl glycoside surfactant which is suitable for the polyaspartic acid, and combines special amino acid, so that the three raw materials generate mutual synergy, can obtain stable and excellent corrosion and fog inhibition effects, can avoid the defects of the raw materials, overcomes the defect of insufficient performance of the conventional environmental protection product, and has obvious practical value.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment relates to a corrosion and fog inhibitor, which comprises the following raw materials:
5-25 kg of polyaspartic acid, yellowish to reddish brown viscous liquid, pH 7.0-9.0 and average molecular weight 1000-3000;
5-25 kg of amino acid selected from lysine, arginine and histidine;
1-5 kg of alkyl glycoside surfactant selected from APG0810 and APG 0814;
45-79 kg of water is prepared into 100kg of corrosion and fog inhibitor.
The preparation method comprises the following specific steps:
a-1, adding 75kg of L-aspartic acid into a polymerization reaction kettle, then adding 0.75-1.9 kg of catalyst phosphoric acid, fully and uniformly stirring, heating for polymerization under the condition of continuous stirring at 20-30 rpm, controlling the polymerization temperature to be 160 +/-5 ℃ and the polymerization time to be 1-3 hours;
a-2, after the polymerization reaction is finished and the reaction materials are cooled to room temperature, transferring the reaction materials into a hydrolysis kettle added with 100kg of water, adding 49-56 kg of ammonia water with the mass fraction of 20% for hydrolysis reaction, controlling the ammonia water to be added at a constant speed within 1-2 h, controlling the pH value in the hydrolysis process to be 10.5-11.0, after the ammonia water is completely dissolved, keeping the temperature of 50-60 ℃, continuing stirring for 1-2 h, and finishing the reaction to obtain a product, namely polyaspartic acid;
b. and (b) taking the polyaspartic acid prepared in the step a-2, adding the total amount of water, adding the total amount of alkyl glycoside surfactant, stirring and dissolving, and finally adding the total amount of amino acid, and fully and uniformly stirring to obtain a light yellow to reddish brown transparent solution, namely the hydrochloric acid pickling corrosion inhibition fog inhibitor.
The following table 1 shows the composition ratios of the raw materials, the preparation conditions, and other factors of each specific example.
The corrosion and fog inhibitor obtained in the above example is subjected to effect verification, the metal corrosion rate is measured by a weight loss method, the fog inhibitor effect is measured by an atmospheric sampling neutralization titration method, and the corrosion and fog inhibitor effects on low-carbon steel in a 20% hydrochloric acid pickling experiment are compared and shown in table 2.
As can be seen from the table above, the hydrochloric acid pickling corrosion and fog inhibitor has the advantages of no toxicity, no harm, environmental protection, easy degradation, small dosage and obvious corrosion and fog inhibiting effect.
Example 2
This example relates to the effect of polyaspartic acid obtained under different preparation conditions on the effectiveness of corrosion-inhibiting fog inhibitor. The preparation of polyaspartic acid adopts the method of polymerization and alkali hydrolysis by L-aspartic acid, and the specific preparation conditions and the using effect are shown in the following table 3.
Comparative example 1
The comparative example is used for testing the using effect of the corrosion-inhibiting fog inhibitor prepared by the polyaspartic acid sample purchased from the market, the surfactant and the amino acid, and the result is shown in the following table 4.
Comparative example 2
The comparative example is used for testing the effects of the raw material components used in the invention on corrosion inhibition and fog inhibition, and the effects of the polyaspartic acid prepared by the invention, the alkyl glycoside surfactant and other amino acids on corrosion inhibition and fog inhibition, and the results are shown in the following table 5.
Comparing examples 1 and 2 with comparative examples 1 and 2, it can be seen that the hydrochloric acid pickling corrosion and fog inhibitor of the present invention has complementary raw material components, thereby ensuring stable and excellent corrosion and fog inhibiting effects and simultaneously ensuring environmental protection of the product.
Claims (7)
1. The hydrochloric acid pickling corrosion-inhibition fog inhibitor is characterized by comprising the following components in parts by mass:
5-25 parts of polyaspartic acid, 5-25 parts of amino acid, 1-5 parts of alkyl glycoside surfactant and the balance of water; the total mass of the polyaspartic acid and the amino acid is not less than 20 parts;
the polyaspartic acid is obtained by thermal polycondensation of L-aspartic acid at 160 +/-5 ℃ for 1-3 h under the action of catalyst phosphoric acid and hydrolysis by ammonia water, wherein the pH value of the hydrolysis process of the ammonia water is controlled to be 10.5-11.0;
the amino acid is at least one of lysine, arginine and histidine.
2. The pickling corrosion-inhibiting mist suppressant of claim 1, wherein: the average molecular weight of the polyaspartic acid is 1000-3000.
3. The pickling corrosion-inhibiting mist suppressant of claim 1, wherein: the alkyl glycoside surfactant is APG0810 or/and APG 0814.
4. The pickling corrosion-inhibiting mist suppressant of claim 1, wherein: the usage amount of the corrosion inhibition fog inhibitor is 0.1-0.5%.
5. A preparation method of the hydrochloric acid pickling corrosion and fog inhibitor as described in any one of claims 1 to 4, characterized by comprising the following steps:
a-1, adding L-aspartic acid into a polymerization reaction kettle, then adding a catalyst phosphoric acid, fully and uniformly stirring, heating for polymerization under a continuous stirring state, controlling the polymerization temperature to be 160 +/-5 ℃ and the polymerization time to be 1-3 h;
a-2, after the polymerization reaction is finished and the reaction materials are cooled to room temperature, adding ammonia water into the reaction materials for hydrolysis reaction, controlling the pH value in the hydrolysis process to be 10.5-11.0, after the materials are completely dissolved, keeping the temperature to be 50-60 ℃, continuously stirring for 1-2 hours, and finishing the reaction to obtain a product, namely polyaspartic acid;
b. and (b) mixing the polyaspartic acid with the average molecular weight of 1000-3000, which is prepared in the step a-2, with an alkyl glycoside surfactant, adding amino acid, and fully and uniformly stirring to obtain a light yellow to reddish brown transparent solution, namely the hydrochloric acid pickling corrosion inhibition fog inhibitor.
6. The method for preparing the hydrochloric acid pickling corrosion-inhibition fog inhibitor according to claim 5, characterized in that: the adding amount of the catalyst phosphoric acid in the step a-1 accounts for 1-2.5% of the mass of the L-aspartic acid.
7. The method for preparing the hydrochloric acid pickling corrosion-inhibition fog inhibitor according to claim 5, characterized in that: and a step a-2, wherein the mass fraction of the ammonia water is 20%, the adding amount of the ammonia water is 65-75% of the mass of the L-aspartic acid, and the ammonia water is controlled to be added at a constant speed within 1-2 h.
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| CN202011579022.XA CN112795927A (en) | 2020-12-28 | 2020-12-28 | Hydrochloric acid pickling corrosion-inhibition fog inhibitor and preparation method thereof |
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Citations (6)
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| US5770553A (en) * | 1993-12-11 | 1998-06-23 | Basf Aktiengesellschaft | Use of polyaspartic acid in detergents and cleaners |
| CN102627359A (en) * | 2012-04-24 | 2012-08-08 | 湖南省电力公司科学研究院 | Phosphorus-free composite corrosion and scale inhibitor containing natural biodegradable substances |
| CN103724625A (en) * | 2014-01-02 | 2014-04-16 | 山东省泰和水处理有限公司 | New process for synthesizing polyaspartic acid through L-asparaginic acid |
| CN106811757A (en) * | 2017-01-23 | 2017-06-09 | 江苏理工学院 | Acid mist inhibitor for hydochloric acid pickling and its application that a kind of normal temperature is used |
| CN106868518A (en) * | 2017-03-27 | 2017-06-20 | 刘雄杰 | Environment-friendly type hydrochloric acid cleans corrosion-retarding fog inhibitor |
| CN110201550A (en) * | 2019-06-24 | 2019-09-06 | 营口科林膜技术工程服务有限公司 | A kind of corrosion inhibiting and descaling agent for reverse osmosis membrane |
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2020
- 2020-12-28 CN CN202011579022.XA patent/CN112795927A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770553A (en) * | 1993-12-11 | 1998-06-23 | Basf Aktiengesellschaft | Use of polyaspartic acid in detergents and cleaners |
| CN102627359A (en) * | 2012-04-24 | 2012-08-08 | 湖南省电力公司科学研究院 | Phosphorus-free composite corrosion and scale inhibitor containing natural biodegradable substances |
| CN103724625A (en) * | 2014-01-02 | 2014-04-16 | 山东省泰和水处理有限公司 | New process for synthesizing polyaspartic acid through L-asparaginic acid |
| CN106811757A (en) * | 2017-01-23 | 2017-06-09 | 江苏理工学院 | Acid mist inhibitor for hydochloric acid pickling and its application that a kind of normal temperature is used |
| CN106868518A (en) * | 2017-03-27 | 2017-06-20 | 刘雄杰 | Environment-friendly type hydrochloric acid cleans corrosion-retarding fog inhibitor |
| CN110201550A (en) * | 2019-06-24 | 2019-09-06 | 营口科林膜技术工程服务有限公司 | A kind of corrosion inhibiting and descaling agent for reverse osmosis membrane |
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