CN115894599A - Camellia oleifera cake extract and application thereof in metal corrosion inhibition - Google Patents
Camellia oleifera cake extract and application thereof in metal corrosion inhibition Download PDFInfo
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- CN115894599A CN115894599A CN202211624645.3A CN202211624645A CN115894599A CN 115894599 A CN115894599 A CN 115894599A CN 202211624645 A CN202211624645 A CN 202211624645A CN 115894599 A CN115894599 A CN 115894599A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 86
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 37
- 239000000284 extract Substances 0.000 title claims abstract description 29
- 241000526900 Camellia oleifera Species 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000018597 common camellia Nutrition 0.000 claims abstract description 22
- 241001122767 Theaceae Species 0.000 claims abstract description 18
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 16
- 229930182490 saponin Natural products 0.000 claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000008247 solid mixture Substances 0.000 claims abstract description 4
- 241000209507 Camellia Species 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 20
- 240000001548 Camellia japonica Species 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 10
- 239000010962 carbon steel Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention belongs to the technical field of corrosion inhibitors, and relates to a camellia oleifera cake extract and application thereof in metal corrosion inhibition. The solid mixture is extracted from the oil-tea camellia cake dregs of the oil-tea camellia processing residues by adopting water, ethanol or a mixed solution of the water and the ethanol as a solvent. As the molecular structure of the tea saponin which is the main component of the mixture contains a large number of unsaturated covalent bonds such as-OH, -COOH, -COOR, C = C and the like, and the heteroatoms have higher electron density as adsorption centers, pi bonds and feedback pi bonds are generated between tea saponin molecules and metals, so that effective passivation films are formed on the surfaces of the metals to prevent the occurrence of electrochemical reactions, and the effect of retarding the corrosion of the metals is achieved. The product belongs to a natural plant extract extracted from waste oil-tea camellia cakes, has the characteristics of low cost, environmental friendliness, wide source, no toxicity and the like, is suitable for industrial pickling of any metal and products thereof, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of corrosion inhibitors, and relates to a camellia oleifera cake extract and application thereof in metal corrosion inhibition.
Background
Metallic materials play a crucial role in the development of one country and its long-term progress in the global economy. However, in any application, the consequences of the interaction of the metal and its articles with the surrounding environment cannot be completely ignored.
Metals and their articles exhibit a high susceptibility to corrosion due to the presence of an acidic environment. Metals and their products are easily corroded in acidic solutions because acids can act on the metal surface through interfacial reactions and cause it to dissolve (release ions), which occurs in various industrial operations. Acid solutions have been widely used in industrial cleaning units such as industrial acid descaling, acid cleaning, acid pickling, and removal of scale from metal surfaces. In addition, corrosion of pipelines during oil and gas transportation may be related to the properties of crude oil and the acidic environment, and dangerous components such as naphthenic acid and sulfur contained in crude oil and acid in the acidic environment may cause corrosion. Typically, corrosion can lead to catastrophic failure of some structures, such as rapid corrosion of metal parts. The lack of corrosion protection has been reported to cause repair, maintenance and repair problems and the cost of replacing damaged equipment has increased year by year.
In the science and engineering of corrosion protection, various methods such as material selection, electrochemical methods, coating deposition, and corrosion inhibitor applications are used. Currently, the use of corrosion inhibitors is the most economical and convenient one of these methods. Various organic or inorganic corrosion inhibitors are used to inhibit corrosion of metals and their products. For example, inorganic chemicals, particularly chromates and their derivatives, have been recognized for their strong inhibitory properties. However, their use is limited due to their toxicity and detrimental effects on human life and the ecological system. On the other hand, the organically synthesized chemical corrosion inhibitors also suffer from development bottlenecks due to their own toxic effects or the adverse effects on the environment caused by their synthesis process.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a metal corrosion inhibitor which is non-toxic to the environment and has a high-efficiency corrosion protection effect on metals and products thereof.
Disclosure of Invention
In view of the above, the present invention provides a natural, green, and inexpensive pickling corrosion inhibitor for preventing unnecessary general corrosion and local corrosion of metals and related products during pickling, and applications thereof.
It is noted that natural products, such as plant extracts, have wide sources, are green and non-toxic, and have low cost, and the like, so that the research on green chemistry and the application of corrosion inhibitors are increased. The researchers have conducted a lot of corrosion inhibition studies on extracts of different parts of plants, and found that bioactive chemical substances contained in the plant extracts are as effective as synthetic chemical corrosion inhibitors. Therefore, the tea saponin is obtained from the waste cake of the oil tea and is used for inhibiting corrosion of metal and products thereof, so that the residues in the oil tea processing industry can be utilized in a high-value manner, and a green environment-friendly corrosion inhibitor which has wide source, low cost and no toxic or harmful effect on the environment can be obtained.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention aims to provide a camellia oleifera cake extract and a simple and efficient preparation method thereof.
Specifically, the camellia oleifera cake extract is a solid mixture extracted from camellia oleifera cake residues by using water, ethanol or a mixed solution of water and ethanol as a solvent;
the mixture contains 60-90% of natural surfactant tea saponin, and the structural formula of the tea saponin is as follows:
it is worth to say that the solid mixture extracted from the oil-tea camellia cake dregs of the oil-tea camellia processing residues is obtained by adopting water, ethanol or a mixed solution of the water and the ethanol as a solvent. The mixture mainly contains natural surfactant-tea saponin, and the content is about 60-90%. As the molecular structure of the tea saponin as the main component contains a large number of unsaturated covalent bonds such as-OH, -COOH, -COOR, C = C and the like, and the heteroatoms as the adsorption centers have higher electron density, pi bonds and feedback pi bonds are generated between tea saponin molecules and metals, so that effective passivation films are formed on the surfaces of the metals to prevent the occurrence of electrochemical reactions, and the effect of retarding the corrosion of the metals is achieved.
Moreover, the product belongs to a natural plant extract extracted from waste oil-tea camellia cakes, has the characteristics of low cost, environmental friendliness, wide source, no toxicity and the like, is suitable for industrial pickling of any metal and products thereof, and has wide application prospect.
Further, the specific operation of extracting the camellia oleifera cake extract is as follows:
carrying out vacuum drying on the oil-tea camellia cake, crushing, sieving by a 80-mesh sieve, and then mixing the oil-tea camellia cake with the powder-liquid ratio of 1: (8-20) fully mixing the oil-tea camellia cake powder with a mixed solvent, wherein the leaching temperature is 25-65 ℃, and the leaching time is 1-4 h; centrifuging, namely performing rotary evaporation on the supernatant obtained by centrifuging for 1-2 h, and standing for 12h; filtering, and freeze-drying the obtained filter cake to obtain an oil-tea camellia cake extract;
wherein the mixed solvent is prepared by mixing water and ethanol according to a volume ratio of 1: (0-100).
The preparation method of the camellia oleifera cake extract has the following characteristics: the preparation method is simple, efficient and feasible, the product is green, environment-friendly and non-toxic, and the crude product can be used as a metal corrosion inhibitor.
The invention also aims to provide the application of the camellia oleifera cake extract in metal corrosion inhibition so as to realize efficient green corrosion prevention on metals and products thereof.
Further, the oil tea cake extract can inhibit corrosion or consumption of the metal plate and the product thereof in the acid washing process.
The specific operation is as follows:
1) Weighing 50-500 mg of the camellia oleifera cake extract as claimed in claim 1, fully dissolving in an acid pickling solution, and metering to 1000mL to obtain a corrosion inhibition solution;
2) Carrying out a carbon steel coupon weight loss experiment in the corrosion inhibition solution prepared in the step 1) at the temperature of 10-50 ℃ to evaluate the corrosion inhibition performance.
Wherein the acid washing solution is a dilute hydrochloric acid or dilute sulfuric acid solution with the concentration of 0.01-3M;
and putting a metal plate to be cleaned into the corrosion inhibition solution, and immersing for 0.5-72h.
According to the technical scheme, compared with the prior art, the camellia oleifera cake extract and the application thereof in metal corrosion inhibition have the following excellent effects:
(1) The metal corrosion inhibitor product of the invention has simple extraction production process, mild and controllable conditions, lower energy consumption and easy industrial production.
(2) The metal corrosion inhibitor product is extracted from oil-tea camellia cake dregs, the raw materials are derived from oil-tea camellia processing residues, the high-value utilization of solid wastes is achieved, and the obtained product is a green corrosion inhibitor product which is low in cost, environment-friendly, non-toxic and harmless, conforms to the green development trend of metal corrosion inhibitors, and has a wide application prospect.
(3) The metal corrosion inhibitor is applied to cleaning products such as carbon steel, metal copper and alloy thereof, can effectively slow down the harmful corrosion of acid to a metal matrix and the excessive consumption of the acid, and has the outstanding advantages of wide source, low cost, low consumption, high corrosion inhibition efficiency, obvious corrosion inhibition effect and the like compared with the current common corrosion inhibitor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of 60% tea saponin.
FIG. 2 is an infrared spectrum of 90% tea saponin.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings of the specification, and it is obvious 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.
The embodiment of the invention discloses a camellia oleifera cake extract and application thereof in metal corrosion inhibition.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention should not be construed as being limited thereto, and the insubstantial modifications and variations of the present invention as shown in the above-described summary of the invention are considered to fall within the scope of the invention by those skilled in the art.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
(1) Carrying out vacuum drying on the oil-tea camellia cake, crushing, sieving by a 80-mesh sieve, and then mixing the oil-tea camellia cake with the powder-liquid ratio of 1:10 mixing oil-tea camellia cake powder with 80% ethanol solvent (V) Ethanol ：V Water (W) = 4:1) and the leaching temperature is 50 ℃, the leaching time is 2h; centrifuging, and centrifugingRotationally evaporating the supernatant for 1h, and standing for 12h; filtering, and freeze-drying the obtained filter cake to obtain the camellia oleifera cake extract with the tea saponin content of 90%.
(2) 1M dilute hydrochloric acid is used for preparing acid washing solutions with the corrosion inhibitor concentrations of 50mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L and 500mg/L respectively. And (3) carrying out corrosion inhibition on carbon steel at the temperature of 35 ℃, immersing for 20 hours, and then carrying out a hanging piece weight loss experiment.
According to the formula:
calculating the efficiency of corrosion inhibition, wherein C RO For metal corrosion inhibition without adding corrosion inhibitor, C R Calculating the corrosion inhibition efficiency for the metal corrosion inhibition rate with the addition of the corrosion inhibitor, wherein C RO For metal corrosion inhibition rate without adding corrosion inhibitor, C R The corrosion inhibition rate of the metal added with the corrosion inhibitor is high.
Example 2
(1) Carrying out vacuum drying on the oil-tea camellia cake, crushing, sieving by a 80-mesh sieve, and then mixing the oil-tea camellia cake with the powder-liquid ratio of 1:10, fully mixing the camellia oleifera cake powder with water, wherein the leaching temperature is 65 ℃, and the leaching time is 4 hours; centrifuging, performing rotary evaporation on the supernatant obtained by centrifuging for 2h, and standing for 12h; filtering, and freeze-drying the obtained filter cake to obtain the camellia oleifera cake extract with the tea saponin content of 60%.
(2) 0.5M dilute hydrochloric acid is used for preparing acid washing solutions with the corrosion inhibitor concentrations of 50mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L and 500mg/L respectively. And (3) carrying out corrosion inhibition on carbon steel at the temperature of 25 ℃, immersing for 10 hours, and then carrying out a hanging piece weight loss experiment.
According to the formula:
calculating the efficiency of corrosion inhibition, wherein C RO For metal corrosion inhibition without adding corrosion inhibitor, C R Calculating the corrosion inhibition efficiency for the metal corrosion inhibition rate with the addition of the corrosion inhibitor, wherein C RO For metal corrosion inhibition without adding corrosion inhibitor, C R The corrosion inhibition speed of the metal added with the corrosion inhibitor is high.
The corrosion inhibition rate of the camellia oleifera cake extract prepared in the two examples on carbon steel in an acid solution is shown in the following table:
table 1 example 1
Table 2 example 2
| Concentration of corrosion inhibitor (mg/L) | Inhibition ratio (%) |
| 50 | 41.65％ |
| 100 | 62.56％ |
| 200 | 71.89％ |
| 300 | 83.35％ |
| 400 | 90.67％ |
| 500 | 93.43％ |
The results of example 1 and example 2 show that the corrosion inhibition efficiency of carbon steel in the pickling solution increases with increasing concentration of the camellia oleifera cake extract. Under experimental conditions, the corrosion inhibition efficiency of the oil-tea camellia cake extract as a metal corrosion inhibitor is better than that of most other plant corrosion inhibitors. The main component tea saponin in the camellia oleifera cake extract is probably due to the fact that a molecular structure of the tea saponin contains a large number of active groups such as-OH, -COOH, -COOR, C = C and the like, and the active groups can act with iron active sites on the surface of carbon steel, so that the active groups are chemically adsorbed on the surface of the carbon steel to form a layer of passivation film, comprehensive or local corrosion of the carbon steel is further prevented, and a good corrosion inhibition effect is achieved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The camellia oleifera cake extract is characterized in that the camellia oleifera cake extract is a solid mixture extracted from camellia oleifera cake residues of camellia oleifera processing residues by using water, ethanol or a mixed solution of water and ethanol as a solvent;
the mixture contains 60-90% of natural surfactant tea saponin, and the structural formula of the tea saponin is as follows:
2. the camellia oleifera cake extract according to claim 1, wherein the specific operation of leaching the camellia oleifera cake extract is as follows:
carrying out vacuum drying on the oil-tea camellia cake, crushing, sieving by a 80-mesh sieve, and then mixing the oil-tea camellia cake with the powder-liquid ratio of 1: (8-20) fully mixing the oil-tea camellia cake powder with water, ethanol or a mixed solvent of the water and the ethanol, wherein the extraction temperature is 25-65 ℃, and the extraction time is 1-4 hours; centrifuging, namely performing rotary evaporation on the supernatant obtained by centrifuging for 1-2 h, and standing for 12h; filtering, and freeze-drying the obtained filter cake to obtain a camellia oleifera cake extract;
wherein the mixed solvent is prepared by mixing water and ethanol according to a volume ratio of 1: (0-100).
3. Use of the camellia oleifera cake extract of claim 1 for metal corrosion inhibition.
4. The use according to claim 3, wherein the Camellia cake extract is capable of inhibiting corrosion or consumption of metal sheets and products thereof during pickling.
5. The use according to claim 4, characterized in that the specific operations are as follows:
1) Weighing 50-500 mg of the camellia oleifera cake extract as claimed in claim 1, fully dissolving in an acid pickling solution, and metering to 1000mL to obtain a corrosion inhibition solution;
2) Carrying out a carbon steel coupon weight loss experiment in the corrosion inhibition solution prepared in the step 1) at the temperature of 10-50 ℃ to evaluate the corrosion inhibition performance.
6. Use according to claim 5, characterized in that the pickling solution is a dilute hydrochloric acid or a dilute sulfuric acid solution with a concentration of 0.01-3M.
7. Use according to claim 5 or 6, characterized in that the metal sheet to be cleaned is placed in the corrosion-inhibiting solution and immersed for 0.5-72 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706863A (en) * | 2005-05-12 | 2005-12-14 | 中国农业科学院油料作物研究所 | Ultrasonic process of preparing theasaponin |
| CN103194762A (en) * | 2013-04-28 | 2013-07-10 | 贵州民族大学 | Plant type green pickling corrosion inhibitor and preparation method and usage method thereof |
| CN109811350A (en) * | 2019-03-02 | 2019-05-28 | 贵州民族大学 | A kind of compound restrainer of barbadosnut pulp extract and preparation method thereof |
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- 2022-12-16 CN CN202211624645.3A patent/CN115894599A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706863A (en) * | 2005-05-12 | 2005-12-14 | 中国农业科学院油料作物研究所 | Ultrasonic process of preparing theasaponin |
| CN103194762A (en) * | 2013-04-28 | 2013-07-10 | 贵州民族大学 | Plant type green pickling corrosion inhibitor and preparation method and usage method thereof |
| CN109811350A (en) * | 2019-03-02 | 2019-05-28 | 贵州民族大学 | A kind of compound restrainer of barbadosnut pulp extract and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 卢基林: "水解油茶饼粕制取酸洗缓蚀剂", 湖南化工, no. 03 * |
| 吴伟明;程明焱;杜海燕;路民旭;王春梅;: "油茶粕缓蚀剂的研制及其缓蚀性能评价", 腐蚀与防护, no. 10 * |
| 林开涵: "茶皂素作为碳钢酸洗缓蚀剂的研究", 福州大学学报(自然科学版), no. 04, pages 2 * |
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| 邓桂兰, 彭超英, 卢峰: "油茶饼粕的综合利用研究", 广州食品工业科技, no. 03 * |
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