CN103194762A - Plant type green pickling corrosion inhibitor and preparation method and usage method thereof - Google Patents
Plant type green pickling corrosion inhibitor and preparation method and usage method thereof Download PDFInfo
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- CN103194762A CN103194762A CN2013101561263A CN201310156126A CN103194762A CN 103194762 A CN103194762 A CN 103194762A CN 2013101561263 A CN2013101561263 A CN 2013101561263A CN 201310156126 A CN201310156126 A CN 201310156126A CN 103194762 A CN103194762 A CN 103194762A
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Abstract
The invention discloses a plant type green pickling corrosion inhibitor and a preparation method and a usage method thereof. The plant type green pickling corrosion inhibitor comprises ingredients of jatropha curcas seed cake hydrolysate. The side product jatropha curcas seed cake after oil is pressed from the jatropha curcas seeds is adopted as materials, the hydrolysate is prepared as the effective ingredient of the corrosion inhibitor, due to the toxicity, a small part of hydrolysate is used as fertilizer for use, and most of hydrolysate is abandoned as wastes; the jatropha curcas is widely planted in the world each country, currently the planting area in China achieves about 8 million hectare, so that the jatropha curcases are rich in sources and low in cost. The corrosion inhibitor is simple in production technique, mild in extraction conditions, low in energy consumption, and easy to operate. The corrosion inhibitor is a natural substance extract, and a biodegradable green non-toxicity and harmless substance, has no influence on the environment compared with the currently chemically synthesized corrosion inhibitor, thereby meeting the development trend of the pickling corrosion inhibitor, being applicable to industrial pickling of carbon steel, aluminum, copper, stainless steel and other products, and having better application prospects.
Description
Technical field
The present invention relates to chemical field, green restrainer of especially a kind of plant type and preparation method thereof and using method.
Background technology
Pickling is widely used in industries such as metallic substance, metallurgy, chemical industry, machinery, is the important means of rust cleaning, scale removal.Acid commonly used has organic acids such as mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and citric acid, thionamic acid.But these acid all have corrosive nature to hardware, and especially the corrodibility of mineral acid is even more serious.For the usage quantity that suppresses metallic corrosion, minimizing acid, the work-ing life of improving pickling effect, prolongation equipment, when carrying out pickling, to add inhibiter.At present inhibiter commonly used mostly is the organic inhibitor of inorganic inhibitor and synthetic, and there are various defectives in they, the cost height that has, and the toxicity that has is bigger, and is big or pollute to the human injury.Along with the enhancing of human environmental consciousness, press for the nontoxic environmental protection high-efficient corrosion inhibitor of exploitation and replace poisonous inhibiter.
Summary of the invention
The objective of the invention is: green restrainer of a kind of plant type and preparation method thereof and using method are provided, and its nontoxic, environmental protection can prevent the etching problem that products such as carbon steel, aluminium occur, to overcome the deficiencies in the prior art in acid cleaning process.
The present invention is achieved in that the green restrainer of plant type, and its composition is the barbadosnut pulp hydrolyzed solution.
The preparation method of the green restrainer of plant type, be that diluted acid and the barbadosnut pulp of 4-6% is the mixed of 6-8:1 by liquid-solid ratio with mass percent concentration, mixture is 80-100 ℃ in temperature to be kept down stirring extracting, extract and filter after 2-10 hour, filtrate is heated concentrated, the reduction in bulk to 1/2 that is concentrated into filtrate gets final product.
Described diluted acid is one or more arbitrary combination of hydrochloric acid, sulfuric acid or nitric acid.
The using method of the green restrainer of plant type, the diluted acid that with the mass percent concentration is 3-10% is pickle solution, the green restrainer of plant type and the diluted acid that add the 1-10% that accounts for diluted acid quality total amount mix, the temperature of mixed solution is controlled at 30-60 ℃, then material to be cleaned is added in the mixed solution, got final product in submergence 2-4 hour.
Described diluted acid is hydrochloric acid, sulfuric acid, nitric acid, the arbitrary combination of one or more in phosphoric acid, hydrofluoric acid or the thionamic acid.
Principle of the present invention is: contain not sharing electron element and polar group in the plant amino acid class inhibiter, and hydrophobic group and hydrophilic group acting in conjunction in the structure.These groups be adsorptive type can form very firm complex compound protective membrane in the metallic surface, this layer protective membrane can prevent the further oxidation of metal.Hydrophile amino, carboxyl and hydrophobic-R base in the amino acid, has certain surfactivity, can produce absorption in more active place at metal/solution liquid interface, the result increases the activation energy of surface reaction, the double electrical layers at interface is changed, thereby make negative electrode or anode in the conjugation reaction of corrosion cell be subjected to strong retardance, the speed of metallic corrosion is sharply reduced.In addition, polar group amino, carboxyl are after the absorption of metallic surface, non-polar group-R one end aligns in the metallic surface, form hydrophobic film, stop electric charge or the substance transfer relevant with corrosion reaction, the result makes acidic medium be squeezed out with the metallic surface by the inhibiter molecule to separate, slowed down corrosion of metal speed.The amino acids material has very strong adsorption in the metallic surface, thereby metal is had corrosion mitigating effect preferably.
Owing to adopted technique scheme, compared with prior art, it is material that the present invention adopts the by product barbadosnut pulp after the jatropha curcas seed oil expression, by preparing its hydrolyzed solution as the effective constituent of inhibiter, because it contains toxic, outside the small part as fertilizer sources was used, major part all abandoned, and belongs to waste; Cortex jatrophae is extensively planted in countries in the world, and China's cultivated area reaches nearly 8,000,000 hectares at present, and its source is abundant, cheap.Production technique of the present invention is simple, the extraction conditions gentleness, and energy consumption is low, is easy to go into operation.Inhibiter of the present invention is the crude substance extract, be biodegradable, nontoxic green matter, compare with the inhibiter of present chemosynthesis, environment is not exerted an influence, the trend that meets the restrainer development, industrial acid-washed applicable to carbon steel, aluminium, copper, stainless steel and products thereof has application promise in clinical practice.
Embodiment
Embodiments of the invention 1: the green restrainer of plant type, its composition is the barbadosnut pulp hydrolyzed solution.
The preparation method of the green restrainer of plant type, be that 5% hydrochloric acid and barbadosnut pulp are the mixed of 7:1 by liquid-solid ratio with mass percent concentration, mixture is 90 ℃ in temperature to be kept down stirring extracting, extract and filter after 5 hours, filtrate is heated concentrated, the reduction in bulk to 1/2 that is concentrated into filtrate gets final product.
Embodiments of the invention 2: the preparation method of the green restrainer of plant type, be that 4% hydrochloric acid and barbadosnut pulp are the mixed of 6:1 by liquid-solid ratio with mass percent concentration, mixture is 80 ℃ in temperature to be kept down stirring extracting, extract and filter after 10 hours, filtrate is heated concentrated, the reduction in bulk to 1/2 that is concentrated into filtrate gets final product.
Embodiments of the invention 3: the preparation method of the green restrainer of plant type, be that 6% hydrochloric acid and barbadosnut pulp are the mixed of 8:1 by liquid-solid ratio with mass percent concentration, mixture is 100 ℃ in temperature to be kept down stirring extracting, extract and filter after 2 hours, filtrate is heated concentrated, the reduction in bulk to 1/2 that is concentrated into filtrate gets final product.
Embodiments of the invention 4: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute hydrochloric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 1%, cleans 4 hours under 30 ℃ of conditions.
Method to embodiment 4 is tested, and testing method adopts weight loss method, according to formula:
Corrosion inhibition rate S=(K
0-K
1)/K
0* 100%
K
0-do not add the corrosion rate of inhibiter; K
1-corrosion rate when adding inhibiter.
Test result is 82.6% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 5: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute hydrochloric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 5%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 88.5% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 6: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute hydrochloric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 90.0% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 7: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 3% dilute hydrochloric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 96.7% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 8: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 5% dilute hydrochloric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 96.3% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 9: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 2% diluted hydrofluoric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 60 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 98.1% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 10: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute sulphuric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 60 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 99.5% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 11: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute phosphoric acid is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 60 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 99.3% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 12: the using method of the green restrainer of plant type, be example to clean carbon steel, selecting mass percent concentration for use is that rare thionamic acid of 10% is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 40 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 91.2% for the corrosion inhibition rate to carbon steel.
Embodiments of the invention 13: the using method of the green restrainer of plant type, be example to clean aluminium, selecting volumetric molar concentration for use is that the dilute hydrochloric acid of 1mol/L is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 2 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 96.6% for the corrosion inhibition rate to aluminium.
Embodiments of the invention 14: the using method of the green restrainer of plant type, be example to clean copper, selecting volumetric molar concentration for use is that the dilute hydrochloric acid of 1mol/L is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 98.6% for the corrosion inhibition rate to copper.
Embodiments of the invention 15: the using method of the green restrainer of plant type, be example to clean copper, selecting mass percent concentration for use is that rare nitric acid of 10% is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 97.8% for the corrosion inhibition rate to copper.
Embodiments of the invention 16: the using method of the green restrainer of plant type, be example to clean copper, selecting mass percent concentration for use is that rare thionamic acid of 10% is pickle solution, adds the green restrainer of the plant type that accounts for pickle solution total mass 10%, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is 98.2% for the corrosion inhibition rate to copper.
Comparative Examples 1 of the present invention: be example to clean carbon steel, selecting mass percent concentration for use is that 10% dilute hydrochloric acid is pickle solution, adds urotropine and carries out compositely, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is as shown in table 1:
Comparative Examples 2 of the present invention: it is dilute hydrochloric acid that carbon steel cleans pickle solution, and concentration is 5%, and the adding benzotriazole carries out composite, cleans 4 hours under 30 ℃ of conditions.
Testing method is tested this application method with embodiment 4, and test result is as shown in table 2:
Can find out obviously that from above test result this inhibiter has higher corrosion protection performance to metal, be a kind of environment-friendly corrosion inhibitor that development potentiality is arranged very much.
The green restrainer that the green restrainer that embodiment 4-embodiment 17 adopts adopts embodiment 1 to prepare.
Claims (5)
1. the green restrainer of a plant type, it is characterized in that: its composition is the barbadosnut pulp hydrolyzed solution.
2. the preparation method of the green restrainer of plant type as claimed in claim 1, it is characterized in that: be that diluted acid and the barbadosnut pulp of 4-6% is the mixed of 6-8:1 by liquid-solid ratio with mass percent concentration, mixture is 80-100 ℃ in temperature to be kept down stirring extracting, extract and filter after 2-10 hour, filtrate is heated concentrated under 80 ℃ of conditions, the reduction in bulk to 1/2 that is concentrated into filtrate gets final product.
3. the preparation method of the green restrainer of plant type according to claim 2 is characterized in that: described diluted acid is one or more the arbitrary combination in hydrochloric acid, sulfuric acid or the nitric acid.
4. the using method of the green restrainer of plant type as claimed in claim 1, it is characterized in that: the diluted acid that with the mass percent concentration is 3-10% is pickle solution, the green restrainer of plant type and the diluted acid that add the 1-10% that accounts for diluted acid quality total amount mix, the temperature of mixed solution is controlled at 30-60 ℃, then material to be cleaned is added in the mixed solution, got final product in submergence 2-4 hour.
5. the using method of the green restrainer of plant type according to claim 4, it is characterized in that: described diluted acid is hydrochloric acid, sulfuric acid, nitric acid, the arbitrary combination of one or more in phosphoric acid, hydrofluoric acid or the thionamic acid.
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| CN2013101561263A CN103194762A (en) | 2013-04-28 | 2013-04-28 | Plant type green pickling corrosion inhibitor and preparation method and usage method thereof |
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| CN2013101561263A CN103194762A (en) | 2013-04-28 | 2013-04-28 | Plant type green pickling corrosion inhibitor and preparation method and usage method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106119868A (en) * | 2016-09-07 | 2016-11-16 | 成都理工大学 | A kind of environment-friendly type restrainer, pickle and the preparation method of corrosion inhibiter |
| CN109811351A (en) * | 2019-03-08 | 2019-05-28 | 贵州民族大学 | A kind of preparation method and applications of restrainer |
| CN109881202A (en) * | 2019-03-08 | 2019-06-14 | 楚雄师范学院 | A kind of preparation method of steel surface corrosion inhibition film |
| CN115894599A (en) * | 2022-12-16 | 2023-04-04 | 湖南省林业科学院 | Camellia oleifera cake extract and application thereof in metal corrosion inhibition |
-
2013
- 2013-04-28 CN CN2013101561263A patent/CN103194762A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| SUBHANUL HASAN ANSARI等: ""A Polyestermide Resin from Jatropha curcas Seed Oil for Anticorrosive Coating"", 《BIOTECHNOLOGY RESEARCH AASIA》 * |
| 吴伟明等: ""油茶粕缓蚀剂的研制及其缓蚀性能评价"", 《腐蚀与防护》 * |
| 张光华等: ""水解油菜籽饼粕制取酸洗缓蚀剂"", 《精细化工》 * |
| 曾宪光等: ""一种环保植物型酸洗缓蚀剂的研究"", 《四川理工学院学报（自然科学版）》 * |
| 蔡洁等: ""天然缓蚀剂对碳钢在盐酸液中缓蚀性能的研究"", 《电镀与精饰》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106119868A (en) * | 2016-09-07 | 2016-11-16 | 成都理工大学 | A kind of environment-friendly type restrainer, pickle and the preparation method of corrosion inhibiter |
| CN109811351A (en) * | 2019-03-08 | 2019-05-28 | 贵州民族大学 | A kind of preparation method and applications of restrainer |
| CN109881202A (en) * | 2019-03-08 | 2019-06-14 | 楚雄师范学院 | A kind of preparation method of steel surface corrosion inhibition film |
| CN109811351B (en) * | 2019-03-08 | 2021-10-12 | 贵州民族大学 | Preparation method and application of pickling corrosion inhibitor |
| CN115894599A (en) * | 2022-12-16 | 2023-04-04 | 湖南省林业科学院 | Camellia oleifera cake extract and application thereof in metal corrosion inhibition |
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Application publication date: 20130710 |