CN108339528B - Corncob-based material and application thereof in environmental remediation - Google Patents
Corncob-based material and application thereof in environmental remediation Download PDFInfo
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- CN108339528B CN108339528B CN201810202335.XA CN201810202335A CN108339528B CN 108339528 B CN108339528 B CN 108339528B CN 201810202335 A CN201810202335 A CN 201810202335A CN 108339528 B CN108339528 B CN 108339528B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a corncob-based material and application thereof in environmental remediation, wherein a preparation method of the corncob-based material comprises the following steps: (1) cleaning corncobs, removing impurities, drying to constant weight, and crushing to obtain a material; (2) mixing the ionic liquid and the material obtained in the step (1) at 60-70 ℃, preserving heat for 2-3 hours, adding thioglycolic acid, heating to 85-90 ℃, preserving heat for 4-5 hours, adding water, cooling to room temperature, filtering, washing with water to neutrality to obtain a precipitate; (3) and (3) under the protection of nitrogen or inert gas, preserving the heat of the sediment obtained in the step (2) at the temperature of 450-550 ℃ for 1-2 hours to obtain the corncob-based material.
Description
Technical Field
The invention belongs to the field of materials and environmental protection, and particularly relates to a corncob-based material and application thereof in environmental remediation.
Background
Corncob is an agricultural by-product with large annual output, the annual corn yield of China is more than one hundred million tons, the by-product corncob is about twenty-three tons, and a large amount of corncob is discarded or used as fuel every year, so that great waste is caused. The corn cob has many active functional groups on the surface, such as hydroxyl, carboxyl, amino, etc., and these functional groups can exchange or chemisorb with heavy metal ions. However, the original corncob has low adsorption capacity for heavy metals, and in order to improve the removal rate of the corncob for heavy metals and organic matters in the environment (such as water and soil), the invention provides the ionic liquid and thioglycolic acid modified corncob-based material capable of efficiently removing the heavy metals and the organic matters in the environment.
Disclosure of Invention
The invention provides a corncob-based material, which is characterized in that the preparation method of the corncob-based material comprises the following steps:
(1) cleaning corncobs, removing impurities, drying to constant weight, and crushing to obtain a material;
(2) mixing the ionic liquid and the material obtained in the step (1) at 60-70 ℃, preserving heat for 2-3 hours, adding thioglycolic acid, heating to 85-90 ℃, preserving heat for 4-5 hours, adding water, cooling to room temperature, filtering, washing with water to neutrality to obtain a precipitate;
(3) and (3) under the protection of nitrogen or inert gas, preserving the heat of the sediment obtained in the step (2) at the temperature of 450-550 ℃ for 1-2 hours to obtain the corncob-based material.
The pulverization in the step (1) is preferably pulverized to 40-60 meshes;
in the step (2), the mass ratio of the ionic liquid to the materials to the thioglycolic acid is 15-25: 10: 0.3-0.5, preferably 15-20: 10: 0.3-0.5;
the water in the step (2) is preferably deionized water, and the dosage of the water is 0.5-1.0 time of the mass of the ionic liquid; the ionic liquid is selected from 1-allyl-3-methylimidazole halide salt, preferably 1-allyl-3-methylimidazole chloride salt.
Another embodiment of the present invention provides a method for preparing the above corncob-based material, which is characterized by comprising the steps of:
(1) cleaning corncobs, removing impurities, drying to constant weight, and crushing to obtain a material;
(2) mixing the ionic liquid and the material obtained in the step (1) at 60-70 ℃, preserving heat for 2-3 hours, adding thioglycolic acid, heating to 85-90 ℃, preserving heat for 4-5 hours, adding water, cooling to room temperature, filtering, washing with water to neutrality to obtain a precipitate;
(3) and (3) under the protection of nitrogen or inert gas, preserving the heat of the sediment obtained in the step (2) at the temperature of 450-550 ℃ for 1-2 hours to obtain the corncob-based material.
The pulverization in the step (1) is preferably pulverized to 40-60 meshes;
in the step (2), the mass ratio of the ionic liquid to the materials to the thioglycolic acid is 15-25: 10: 0.3-0.5, preferably 15-20: 10: 0.3-0.5;
the water in the step (2) is preferably deionized water, and the dosage of the water is 0.5-1.0 time of the mass of the ionic liquid; the ionic liquid is selected from 1-allyl-3-methylimidazole halide salt, preferably 1-allyl-3-methylimidazole chloride salt.
Another embodiment of the present invention provides the use of the above-described corncob-based material for environmental remediation.
Another embodiment of the invention provides the application of the corncob-based material in removing heavy metals in soil and water. The heavy metal is preferably hexavalent chromium.
Another embodiment of the present invention provides the use of the above-described corncob-based material for removing pesticide residues. The pesticide is preferably an organochlorine pesticide or a carbamate pesticide. The organochlorine pesticide is preferably chlordane and toxaphenol, and the carbamate pesticide is preferably metolcarb and carbaryl.
Compared with the prior art, the invention has the advantages that: the invention obtains a novel corncob-based material with strong removal effect on heavy metals and pesticides by treating corncobs with ionic liquid and thioglycollic acid. The material is expected to be developed as an environment repairing agent, especially in the aspect of removing heavy metals and pesticide residues.
Drawings
FIG. 1 is an SEM image of product A;
FIG. 2 is a diagram showing the effect of products A-E on removing hexavalent chromium from water.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Cleaning corncob, removing impurities, drying to constant weight, and pulverizing to 40-60 mesh to obtain material (10 kg);
(2) uniformly mixing 1-allyl-3-methylimidazole chloride salt (20kg) with the material (10kg) obtained in the step (1) at the temperature of 60 ℃, preserving heat for 2 hours, adding thioglycolic acid (300g), heating to 85-90 ℃, preserving heat for 5 hours, adding deionized water (10kg), cooling to room temperature, filtering, and washing with water to be neutral to obtain a precipitate;
(3) and (3) keeping the temperature of the sediment obtained in the step (2) at 450 ℃ for 2 hours under nitrogen to obtain the corncob-based material (hereinafter referred to as product A).
Example 2
(1) Cleaning corncob, removing impurities, drying to constant weight, and pulverizing to 40-60 mesh to obtain material (6 kg);
(2) uniformly mixing 1-allyl-3-methylimidazole chloride salt (9kg) with the material (6kg) obtained in the step (1) at 70 ℃, preserving heat for 3 hours, adding thioglycolic acid (300g), heating to 85-90 ℃, preserving heat for 4 hours, adding water (9kg), cooling to room temperature, filtering, and washing with water to be neutral to obtain a precipitate;
(3) and (3) keeping the precipitate obtained in the step (2) at 550 ℃ for 1h under argon to obtain the corncob-based material (hereinafter referred to as product B).
Example 3
(1) Cleaning corncob, removing impurities, drying to constant weight, and pulverizing to 40-60 mesh to obtain material (10 kg);
(2) uniformly mixing 1-allyl-3-methylimidazole chloride salt (20kg) with the material (10kg) obtained in the step (1) at the temperature of 60 ℃, preserving heat for 2 hours, adding acetic acid (300g), heating to 85-90 ℃, preserving heat for 5 hours, adding deionized water (10kg), cooling to room temperature, filtering, and washing with water to be neutral to obtain a precipitate;
(3) and (3) keeping the precipitate obtained in the step (2) at 450 ℃ for 2h under nitrogen to obtain the corncob-based material (hereinafter referred to as product C).
Example 4
(1) Cleaning corncob, removing impurities, drying to constant weight, and pulverizing to 40-60 mesh to obtain material (10 kg);
(2) uniformly mixing 1-allyl-3-methylimidazole chloride salt (20kg) with the material (10kg) obtained in the step (1) at the temperature of 60 ℃, preserving heat for 2 hours, heating to 85-90 ℃, preserving heat for 5 hours, adding deionized water (10kg), cooling to room temperature, filtering, washing with water to be neutral to obtain a precipitate;
(3) and (3) keeping the precipitate obtained in the step (2) at 450 ℃ for 2h under nitrogen to obtain the corncob-based material (hereinafter referred to as product D).
Example 5
(1) Cleaning corncob, removing impurities, drying to constant weight, and pulverizing to 40-60 mesh to obtain material (10 kg);
(2) adding thioglycollic acid (300g) into the material (10kg) obtained in the step (1), uniformly mixing, heating to 85-90 ℃, keeping the temperature for 5 hours, adding deionized water (10kg), cooling to room temperature, filtering, and washing with water to be neutral to obtain a precipitate;
(3) and (3) keeping the precipitate obtained in the step (2) at 450 ℃ for 2h under nitrogen to obtain the corncob-based material (hereinafter referred to as product E).
Example 6 heavy Metal scavenging experiment
(1) Hexavalent chromium removal test in water
Respectively taking 100mL of hexavalent chromium standard solution (20mg/L), respectively adding 15mg of product A, B, C, D, E, and stirring for reaction for 100 min; the experimental result shows that the absorption clearance rate of the product A, B to hexavalent chromium reaches more than 95%, and the effect is far better than that of the product C-E (figure 2).
(2) Lead removal experiment in soil
And (3) respectively taking 100g of lead-containing soil samples (each gram of soil contains 2.5mg of lead), respectively adding 6mg of the product A, C, E, adding water, uniformly mixing to form slurry, adsorbing for 8 hours, respectively supplementing 6mg of the corresponding product A, C, E, uniformly mixing, continuously adsorbing for 6 hours, and then detecting, wherein the result shows that the clearance rate of the product A on the lead in the soil samples reaches 79.6%, the clearance rate of the product C on the lead in the soil samples reaches 36.2%, and the clearance rate of the product E on the lead in the soil samples is lower than 10%.
Example 7 degradation test of pesticide residue in soil
Selecting a soil sample:
sample 1: the contents of chlordane and toxaphenol are both 500 mg/kg;
sample 2: the content of the metolcarb and the carbaryl is 500 mg/kg.
The experimental method comprises the following steps: respectively taking 5 parts of 10kg samples 1 and 2, respectively adding the products A-E (1.5 g each), uniformly mixing to ensure that the water content is 20-30%, respectively supplementing the corresponding products A-E (1.0 g each) after 36 hours, uniformly mixing, and detecting the content of the pesticide in the soil after 36 hours, wherein the results are shown in Table 1.
TABLE 1
Claims (1)
1. The application of corncob-based material in removing heavy metals in soil and water is characterized in that the heavy metals are selected from hexavalent chromium and lead, and the preparation method of the corncob-based material comprises the following steps: (1) cleaning corncobs, removing impurities, drying to constant weight, and crushing to obtain a material; (2) mixing the ionic liquid and the material obtained in the step (1) at 60-70 ℃, preserving heat for 2-3 hours, adding thioglycolic acid, heating to 85-90 ℃, preserving heat for 4-5 hours, adding water, cooling to room temperature, filtering, washing with water to neutrality to obtain a precipitate; (3) preserving the precipitate obtained in the step (2) at the temperature of 450-550 ℃ for 1-2 hours under the protection of nitrogen or inert gas to obtain the corncob-based material; the crushing in the step (1) is to crush to 40-60 meshes; in the step (2), the mass ratio of the ionic liquid to the materials to the thioglycolic acid is 15-20: 10: 0.3-0.5; the water is deionized water, and the dosage of the water is 0.5 to 1.0 time of the mass of the ionic liquid; the ionic liquid is selected from 1-allyl-3-methylimidazole chloride salt.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810202335.XA CN108339528B (en) | 2018-03-10 | 2018-03-10 | Corncob-based material and application thereof in environmental remediation |
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| CN201810202335.XA CN108339528B (en) | 2018-03-10 | 2018-03-10 | Corncob-based material and application thereof in environmental remediation |
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| CN108339528A CN108339528A (en) | 2018-07-31 |
| CN108339528B true CN108339528B (en) | 2021-03-05 |
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- 2018-03-10 CN CN201810202335.XA patent/CN108339528B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Effect of ionic liquid pretreatment on the structure of hemicelluloses from corncob;Shaoni Sun;《J.Agric Food Chem.》;20121024;第60卷(第44期);11120-7 * |
| 响应面法优化巯基纤维素膜去除Cr6+的吸附条件;王静等;《环境科学与技术》;20150630;第38卷(第6期);167-171 * |
| 经离子液体水溶液预处理玉米芯对亚甲基蓝吸附性能的研究;汪雁等;《安徽科技学院学报》;20180115;第32卷(第1期);64-71 * |
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