CN110629229A - Fruit waste compound corrosion inhibitor and preparation method and application thereof - Google Patents
Fruit waste compound corrosion inhibitor and preparation method and application thereof Download PDFInfo
- Publication number
- CN110629229A CN110629229A CN201910979648.0A CN201910979648A CN110629229A CN 110629229 A CN110629229 A CN 110629229A CN 201910979648 A CN201910979648 A CN 201910979648A CN 110629229 A CN110629229 A CN 110629229A
- Authority
- CN
- China
- Prior art keywords
- corrosion inhibitor
- fruit waste
- compound corrosion
- fruit
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- 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
-
- 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
- C23G1/08—Iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a fruit waste compound corrosion inhibitor and a preparation method and application thereof, wherein the fruit waste compound corrosion inhibitor comprises 0.1 ~ 1.0.0 g/L of mangosteen shell extract, 0.05 ~ 0.5.5 g/L of rare earth compound, 0.1 ~ 0.5.5 g/L of anionic surfactant, 0.01 ~ 0.1.1 g/L of polyethylene glycol and the balance of pickling solution.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a fruit waste compound corrosion inhibitor, and a preparation method and application thereof.
Background
Mangosteen (scientific name: Garcinia mangostana L.) is commonly called mangosteen, or mangosteen, mangosteen and mangosteen. Small arbors are 12-20 m high, have many and dense branches, are opposite alternately, and have obvious longitudinal ribs. The blade is thick and leather, and has luster, elliptic or elliptic rectangle and circle shape, short and tapered top end, wide wedge shape at the base part or nearly circular shape. 2-9 of male flowers are clustered to grow the top ends of the branches, and the flower stalks are short; the female flowers grow singly or in pairs, grow on the top ends of the branches and are slightly larger than the male flowers; the ovary is 58 rooms, almost no style, and the stigma is 5-6 deep cracks. The mature fruit has purple red color, yellow brown patches among the fruits, smoothness, 4-5 seeds, lustered and juicy pseudoseed coats and white color. The flowering period is 9-10 months, and the fruit period is 11-12 months. The native Marugu, Asia and African tropical regions are widely cultivated; taiwan, Fujian, Guangdong and Yunnan provinces also have introduction or test seeds. Is a famous tropical fruit and can be eaten raw or preserved. The red pigment in the epicarp can be used to make dyes. The mangosteen shell is discarded as garbage, so that the environment pollution can be caused while the resources are wasted. Most of the pickling corrosion inhibitors aim at the corrosion inhibition of a single acid species and a single metal, have strong specificity, large effect difference, unstable chemical properties, large risk of equipment corrosion accidents due to the fact that the corrosion inhibitors need to be configured on site and have large working strength and are easy to cause misoperation, and most of the corrosion inhibitors have the problems of high price, high toxicity, environmental pollution and the like, so that the development of the compound corrosion inhibitor prepared by using the mangosteen shells of flower plants is very necessary, and the environment-friendly compound corrosion inhibitor can be obtained on the basis of recycling waste.
Disclosure of Invention
The first purpose of the invention is to provide a fruit waste compound corrosion inhibitor; the second purpose is to provide a preparation method of the fruit waste compound corrosion inhibitor; the third purpose is to provide the application of the fruit waste compound corrosion inhibitor.
The first purpose of the invention is realized in such a way that the fruit waste compound corrosion inhibitor comprises 0.1 ~ 1.0.0 g/L of mangosteen shell extract, 0.05 ~ 0.5.5 g/L of rare earth compound, 0.1 ~ 0.5.5 g/L of anionic surfactant, 0.01 ~ 0.1.1 g/L of polyethylene glycol and the balance of pickling solution.
The second purpose of the invention is realized by mixing and stirring the raw materials in the formula ratio uniformly to obtain the target fruit waste compound corrosion inhibitor.
The third purpose of the invention is realized by the application of the fruit waste compound corrosion inhibitor in the pickling of steel materials.
The invention overcomes the defects of high price, high toxicity and environmental pollution of most corrosion inhibitors, and the metal corrosion inhibitor prepared by taking the mangosteen shell which is a fruit waste as a raw material is added with the rare earth compound, the surfactant and the stabilizing agent of polyethylene glycol, and the balance of pickling solution has synergistic effect. The metal corrosion inhibitor provided by the invention has the advantages of no toxicity, low cost, strong adaptability, obvious inhibition of corrosion of acid on metal materials, no pollution after use, and safe and convenient use.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The fruit waste compound corrosion inhibitor comprises 0.1 ~ 1.0.0 g/L of mangosteen shell extract, 0.05 ~ 0.5.5 g/L of rare earth compound, 0.1 ~ 0.5.5 g/L of anionic surfactant, 0.01 ~ 0.1.1 g/L of polyethylene glycol and the balance of pickling solution.
2. The fruit waste compound corrosion inhibitor according to claim 1, characterized in that the rare earth compound is rubidium nitrate.
3. The fruit waste compound corrosion inhibitor according to claim 1, wherein the anionic surfactant is sodium tetradecyl sulfate.
4. The fruit waste compound corrosion inhibitor according to claim 1, wherein the mangosteen shell extract is prepared from the fruit waste mangosteen shell serving as a raw material through the steps of pretreatment, extraction, concentration, extraction and post-treatment, and specifically comprises the following steps:
A. pretreatment: drying, crushing and sieving mangosteen shells to obtain mangosteen shell powder a;
B. extracting, namely adding ethanol solution with the volume 20 ~ 40 times that of the mangosteen shell powder into the mangosteen shell powder a, soaking for 2 ~ 4h at 10 ~ 30 ℃ to obtain a material b, refluxing and extracting the material b in a water bath at the temperature of 50 ~ 80 ℃ for 2 ~ 6h, and performing suction filtration to obtain an extracting solution c;
C. concentrating the extracting solution c to 1/2 ~ 1/3 of the volume of the extracting solution c to obtain a concentrated solution d;
D. extracting, namely adding petroleum ether with the volume 2 ~ 5 times that of the concentrated solution d into the concentrated solution d, fully oscillating, standing for 12 ~ 48h to obtain a petroleum ether layer e and a lower-layer extracting solution f, recovering the petroleum ether layer e, adding petroleum ether with the volume 2 ~ 3 times that of the lower-layer extracting solution f into the lower-layer extracting solution f again, fully oscillating, standing for layering, and replacing the petroleum ether every 10 ~ 30min until the petroleum ether layer is colorless to obtain an extracting solution g;
E. and (3) post-treatment: evaporating and drying the extracting solution g to obtain the target mangosteen shell extract.
5. The fruit waste compound corrosion inhibitor according to claim 4, wherein the drying in the step A comprises air drying and constant temperature drying, specifically, the waste mangosteen shells are dried in an air-blowing oven at 50 ~ 70 ℃ for 48 ~ 60h at constant temperature.
6. The fruit waste compound corrosion inhibitor according to claim 4, wherein the volume concentration of the ethanol solution in the step B is 20 ~ 60%.
7. The fruit waste built corrosion inhibitor according to claim 4, wherein the evaporation in step E is rotary evaporation.
8. The fruit waste compound corrosion inhibitor according to claim 4, wherein the drying in the step E is carried out at the temperature of 50 ~ 70 ℃ for 12 ~ 24 h.
The preparation method of the mangosteen shell extract provided by the invention specifically comprises the following operations:
A. pre-treating, collecting cortex Bambusae, air drying, drying in air oven at 60 deg.C for 48 ~ 60h, taking out, naturally cooling to room temperature, and pulverizing to obtain cortex Bambusae powder with particle size of 300 ~ 1000 μm;
B. extracting by adding 20 ~ 60% ethanol solution at room temperature (10 ~ 30 deg.C) into the mangosteen shell powder, soaking for 2 ~ 4h with a solid-to-liquid ratio of 1:20 ~ 40, and reflux-extracting in 50 ~ 80 deg.C water bath for 2 ~ 6 h;
C. concentrating by vacuum filtering the ethanol extractive solution to remove residue powder of rhizoma Dioscoreae Septemlobae shell, and rotary evaporating the solution at 40 ~ 80 deg.C to 1/2 ~ 1/3 volume;
D. extracting, namely adding petroleum ether with the volume 2 ~ 5 times into the concentrated ethanol extracting solution, fully shaking, standing for 12 ~ 48h, separating the petroleum ether at the upper layer from the extracting solution at the lower layer, recovering the upper layer liquid, adding the lower layer liquid into a separating funnel again, adding petroleum ether with the volume 2 ~ 3 times, fully shaking, standing and layering, and replacing the petroleum ether every 10 ~ 30 minutes until the upper layer liquid is colorless;
E. and (3) performing rotary evaporation on the extracted subnatant to 40 ~ 60ml, putting the evaporated liquid into an evaporation dish, drying the liquid in a forced air drying oven at 50 ~ 70 ℃ for 12 ~ 24h, and shoveling the solid by using a crystal shovel to obtain the target mangosteen shell extract.
The preparation method of the fruit waste compound corrosion inhibitor provided by the invention is characterized in that the target fruit waste compound corrosion inhibitor is obtained by uniformly mixing and stirring the raw materials in the formula ratio.
The application of the fruit waste compound corrosion inhibitor is the application of the fruit waste compound corrosion inhibitor in steel material pickling.
The invention is further illustrated by the following specific examples:
example 1
Preparation of mangosteen Shell extract
A. Pre-treating, collecting cortex Bambusae, air drying, drying in air oven at 60 deg.C ~ 70 deg.C for 60 ~ 72 h, naturally cooling to room temperature, and pulverizing to obtain cortex Bambusae powder with particle size of 150 ~ 2000 μm;
B. extracting by adding 10 ~ 70% ethanol solution at room temperature (5 ~ 35 deg.C) into the mangosteen shell powder, soaking for 2 ~ 6h with a solid-to-liquid ratio of 1:25 ~ 50, and reflux-extracting in 60 ~ 85 deg.C water bath for 3 ~ 9 h;
C. concentrating by vacuum filtering the ethanol extractive solution to remove residue powder of rhizoma Dioscoreae Septemlobae shell, and rotary evaporating the solution at 45 ~ 75 deg.C on rotary evaporator to 1/4 ~ 1/2 volume;
D. extracting, namely adding petroleum ether with the volume 2 ~ 6 times into the concentrated ethanol extracting solution, fully shaking, standing for 15 ~ 60h, separating the petroleum ether at the upper layer from the extracting solution at the lower layer, recovering the upper layer liquid, adding the lower layer liquid into a separating funnel again, adding petroleum ether with the volume 2 ~ 5 times, fully shaking, standing and layering, and replacing the petroleum ether every 20 ~ 40 minutes until the upper layer liquid is colorless;
E. and (3) performing rotary evaporation on the extracted subnatant to 40 ~ 60ml, putting the evaporated liquid into an evaporation dish, drying the liquid in a forced air drying oven at 50 ~ 70 ℃ for 12 ~ 24h, and shoveling the solid by using a crystal shovel to obtain the target mangosteen shell extract.
Example 2
Fruit waste compound metal corrosion inhibitor
Taking 0.10 g of mangosteen shell extract, 0.5g of neodymium nitrate, 0.5g of tetradecyl sodium sulfate and 0.01g of polyethylene glycol in the example 1, adding 1L of hydrochloric acid lotion with the concentration of 0.5 ~ 5.0.0 mol/L, and uniformly stirring to obtain the target compound corrosion inhibitor of fruit waste.
Example 3
Preparation of fruit waste compound corrosion inhibitor for steel acid washing
1.0g of mangosteen shell extract, 0.5g of neodymium nitrate, 0.5g of tetradecyl sodium sulfate and 0.05g of polyethylene glycol in example 1 are taken, 1L of sulfuric acid lotion with the concentration of 0.5 ~ 5.0.0 mol/L is added, and the mixture is uniformly stirred to obtain the target compound corrosion inhibitor of fruit waste.
Example 4
Preparation of fruit waste compound corrosion inhibitor for steel acid washing
1.0g of mangosteen shell extract, 0.5g of neodymium nitrate, 0.5g of tetradecyl sodium sulfate and 0.1g of polyethylene glycol in example 1 are taken, 1L of phosphoric acid lotion with the concentration of 0.5 ~ 10.0.0 mol/L is added, and the mixture is uniformly stirred to obtain the target compound corrosion inhibitor of fruit waste.
Test example 1
Pickling of ferrous Material
The steel material is selected as cold-rolled steel sheet, the corrosion inhibitor compounded in the embodiment 2 is injected and mixed uniformly, the corrosion inhibition performance can be more than 95% at different temperatures (20 ~ 50 ℃ C.) and different corrosion soaking times (6 ~ 156 h), the table 1 shows 1.0 mol/L HCl test data, and the method is a weight loss method.
TABLE 1 Corrosion inhibition rate of plant compound corrosion inhibitor to cold rolled steel in 1.0 mol/L HCl
Test example 2
Pickling of ferrous Material
The steel material is selected as cold-rolled steel sheet, the corrosion inhibitor compounded in the embodiment 3 is injected and mixed uniformly, the corrosion inhibition performance can be more than 94% at different temperatures (20 ~ 50 ℃ C.) and different corrosion soaking times (6 ~ 48 h), the table 2 shows 3.0 mol/L HCl test data, and the method is a weight loss method.
TABLE 2 Corrosion inhibition rate of plant compound corrosion inhibitor to cold rolled steel in 3.0 mol/L HCl
Test example 3
Pickling of ferrous Material
The steel material is selected as cold-rolled steel sheet, the corrosion inhibitor compounded in the embodiment 3 is injected and evenly mixed, the corrosion inhibition performance can be more than 95% at different temperatures (20 ~ 50 ℃) and different corrosion soaking times (6 ~ 96 h), and the table 3 shows that the corrosion inhibition performance is 1.0 mol/L H2SO4Test data, the method is a weight loss method.
TABLE 3 plant Compound Corrosion inhibitor to Cold rolled Steel at 1.0 mol/L H2SO4Middle inhibition rate
Test example 4
Pickling of ferrous Material
The steel material is selected as cold-rolled steel sheet, the corrosion inhibitor compounded in the embodiment 4 is injected and evenly mixed, the corrosion inhibition performance can be more than 95% at different temperatures (20 ~ 50 ℃) and different corrosion soaking times (6 ~ 120 h), and the corrosion inhibition performance is 1.0 mol/L H in a table 43PO4Test data, the method is a weight loss method.
TABLE 4 Compound plant corrosion inhibitor at 1.0 mol/L H for cold rolled steel3PO4Middle inhibition rate
Test example 5
Pickling of ferrous Material
The steel material is selected as cold-rolled steel sheet, the corrosion inhibitor compounded in the embodiment 4 is injected and evenly mixed, the corrosion inhibition performance can be more than 91 percent at different temperatures (20 ~ 50 ℃) and different corrosion soaking times (6 ~ 120 h), and the corrosion inhibition performance is 9.0 mol/L H in the table 43PO4Test data, the method is a weight loss method.
TABLE 4 Compound plant corrosion inhibitor at 9.0 mol/L H for cold rolled steel3PO4Middle inhibition rate
Claims (10)
1. The compound corrosion inhibitor for the fruit wastes is characterized by comprising 0.1 ~ 1.0.0 g/L of mangosteen shell extract, 0.05 ~ 0.5.5 g/L of rare earth compound, 0.1 ~ 0.5.5 g/L of anionic surfactant, 0.01 ~ 0.1.1 g/L of polyethylene glycol and the balance of pickling solution.
2. The fruit waste compound corrosion inhibitor according to claim 1, characterized in that the rare earth compound is rubidium nitrate.
3. The fruit waste compound corrosion inhibitor according to claim 1, wherein the anionic surfactant is sodium tetradecyl sulfate.
4. The fruit waste compound corrosion inhibitor according to claim 1, wherein the mangosteen shell extract is prepared from the fruit waste mangosteen shell serving as a raw material through the steps of pretreatment, extraction, concentration, extraction and post-treatment, and specifically comprises the following steps:
A. pretreatment: drying, crushing and sieving mangosteen shells to obtain mangosteen shell powder a;
B. extracting, namely adding ethanol solution with the volume 20 ~ 40 times that of the mangosteen shell powder into the mangosteen shell powder a, soaking for 2 ~ 4h at 10 ~ 30 ℃ to obtain a material b, refluxing and extracting the material b in a water bath at the temperature of 50 ~ 80 ℃ for 2 ~ 6h, and performing suction filtration to obtain an extracting solution c;
C. concentrating the extracting solution c to 1/2 ~ 1/3 of the volume of the extracting solution c to obtain a concentrated solution d;
D. extracting, namely adding petroleum ether with the volume 2 ~ 5 times that of the concentrated solution d into the concentrated solution d, fully oscillating, standing for 12 ~ 48h to obtain a petroleum ether layer e and a lower-layer extracting solution f, recovering the petroleum ether layer e, adding petroleum ether with the volume 2 ~ 3 times that of the lower-layer extracting solution f into the lower-layer extracting solution f again, fully oscillating, standing for layering, and replacing the petroleum ether every 10 ~ 30min until the petroleum ether layer is colorless to obtain an extracting solution g;
E. and (3) post-treatment: evaporating and drying the extracting solution g to obtain the target mangosteen shell extract.
5. The fruit waste compound corrosion inhibitor according to claim 4, wherein the drying in the step A comprises air drying and constant temperature drying, specifically, the waste mangosteen shells are dried in an air-blowing oven at 50 ~ 70 ℃ for 48 ~ 60h at constant temperature.
6. The fruit waste compound corrosion inhibitor according to claim 4, wherein the volume concentration of the ethanol solution in the step B is 20 ~ 60%.
7. The fruit waste built corrosion inhibitor according to claim 4, wherein the evaporation in step E is rotary evaporation.
8. The fruit waste compound corrosion inhibitor according to claim 4, wherein the drying in the step E is carried out at the temperature of 50 ~ 70 ℃ for 12 ~ 24 h.
9. A preparation method of the fruit waste compound corrosion inhibitor of claim 1 ~ 8 is characterized in that the target fruit waste compound corrosion inhibitor is obtained by uniformly mixing and stirring the raw materials in the formula ratio.
10. The application of the fruit waste compound corrosion inhibitor of claim 1 ~ 8, wherein the fruit waste compound corrosion inhibitor is applied to pickling of steel materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910979648.0A CN110629229A (en) | 2019-10-15 | 2019-10-15 | Fruit waste compound corrosion inhibitor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910979648.0A CN110629229A (en) | 2019-10-15 | 2019-10-15 | Fruit waste compound corrosion inhibitor and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110629229A true CN110629229A (en) | 2019-12-31 |
Family
ID=68976550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910979648.0A Pending CN110629229A (en) | 2019-10-15 | 2019-10-15 | Fruit waste compound corrosion inhibitor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110629229A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101629336B1 (en) * | 2015-09-02 | 2016-06-10 | (주)아인스 | Method for cleaning aluminum member |
| CN105755484A (en) * | 2016-05-14 | 2016-07-13 | 西南林业大学 | High-efficient compounding plant inhibitor as well as preparation method and application thereof |
-
2019
- 2019-10-15 CN CN201910979648.0A patent/CN110629229A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101629336B1 (en) * | 2015-09-02 | 2016-06-10 | (주)아인스 | Method for cleaning aluminum member |
| CN105755484A (en) * | 2016-05-14 | 2016-07-13 | 西南林业大学 | High-efficient compounding plant inhibitor as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YULI RIZKY ANANDA NASUTION.ET.AL.: "PENENTUAN EFISIENSI INHIBISI REAKSI KOROSI BAJA MENGGUNAKAN EKSTRAK KULIT BUAH MANGGIS (Garcinia mangostana L)", 《JURNAL TEKNIK KIMIA USU》 * |
| 李向红等: "核桃青皮提取物和木质素磺酸钠对冷轧钢在H3PO4溶液中的缓蚀协同效应", 《第十届全国腐蚀大会》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105755484B (en) | A kind of highly efficiency compositional plant corrosion inhibiter and preparation method and application | |
| CN102167635B (en) | Nutritious and high efficient foliar fertilizer for growth of humic acid plant and preparation method thereof | |
| CN101485343A (en) | Extraction technology of active ingredients of enteromorpha and preparation method of enteromorpha seaweed fertilizer | |
| CN104312627B (en) | A kind of crystallization process removes solvent and the method for resin in montanin wax | |
| CN104262009B (en) | Folium Agaves Sisalanae waste water produces the method for Semen Maydis Liquid Fertilizer | |
| CN105948943A (en) | Special antifreezing foliage fertilizer for garlic and application thereof | |
| CN111153737A (en) | Efficient composite water-soluble fertilizer and preparation method and application thereof | |
| CN105010391A (en) | Rice cadmium reduction agent | |
| CN110983344A (en) | Camellia oleifera shell compound corrosion inhibitor and preparation method and application thereof | |
| CN110552011A (en) | Invasive weed compound corrosion inhibitor and preparation method and application thereof | |
| CN103897734B (en) | A kind of crude montan wax efficient energy-saving deresination method and device | |
| CN110629229A (en) | Fruit waste compound corrosion inhibitor and preparation method and application thereof | |
| CN113185360A (en) | Plant nutrient solution for remarkably improving yield and efficiency of plants and preparation method thereof | |
| CN105557399B (en) | With offal to the method for fruit tree insect prevention | |
| CN104861737B (en) | A kind of preparation method of sophora flower vegetable colour | |
| CN110592599A (en) | Economic forest waste compound metal corrosion inhibitor and preparation method and application thereof | |
| CN110552010A (en) | Flower plant compound corrosion inhibitor and preparation method and application thereof | |
| CN110607529A (en) | Malignant weed compound corrosion inhibitor and preparation method and application thereof | |
| CN110565098A (en) | Invasive plant compound metal corrosion inhibitor and preparation method and application thereof | |
| CN109258356A (en) | Inhibit the method for rice absorbing arsenic cadmium using gypsum composite | |
| CN110878416A (en) | Coffee shell compound corrosion inhibitor and preparation method and application thereof | |
| CN111020603A (en) | Rapeseed cake meal compound corrosion inhibitor and preparation method and application thereof | |
| CN108208033A (en) | A kind of preparation method of the botanical fungicide composition of the shell extract containing Chinese prickly ash | |
| CN113549919B (en) | Tagetes extract compound corrosion inhibitor and preparation method and application thereof | |
| CN110952105A (en) | Jatropha curcas cake meal compound corrosion inhibitor and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191231 |
|
| RJ01 | Rejection of invention patent application after publication |