CN110788127B - Nano carbon composite material with soil remediation function and soil improvement method - Google Patents
Nano carbon composite material with soil remediation function and soil improvement method Download PDFInfo
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- CN110788127B CN110788127B CN201911109123.8A CN201911109123A CN110788127B CN 110788127 B CN110788127 B CN 110788127B CN 201911109123 A CN201911109123 A CN 201911109123A CN 110788127 B CN110788127 B CN 110788127B
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
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Abstract
The invention relates to the technical field of soil remediation, and particularly discloses a nano carbon composite material with a soil remediation function and a soil improvement method. The nano carbon composite material with the soil remediation function comprises the following components in parts by weight: 50-70 parts of diatomite; 20-30 parts of carbon materials are recovered in sewage treatment; 5-10 parts of carbon nanotubes; 5-10 parts of calcium hydroxide. The nano carbon composite material has excellent heavy metal removal capacity; in addition, the carbon material is recovered in the sewage treatment, so that the components in the aquaculture sewage are adsorbed, and the nano carbon composite material can be used in soil to increase the fertility of the soil.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a nano carbon composite material with a soil remediation function and a soil improvement method.
Background
Soil remediation refers to the restoration of the polluted soil to normal by using a remediation technology; with the acceleration of industrialization, the discharge of irregular sewage and sludge can cause serious soil pollution. Heavy metal contamination is one of the types of soil contamination; particularly, heavy metals have high toxicity, cannot be degraded by soil when discharged into the soil, and are generally difficult to remove. After crops are planted in the soil polluted by the heavy metals, the heavy metals are transferred to the crops and then absorbed by human bodies, and the human health is affected. The common heavy metals of cadmium and lead are easy to be absorbed by other crops, thereby further harming the health of people.
In soil remediation technology, the addition of a soil remediation agent to contaminated soil is a common remediation method. However, the existing soil remediation agent with good effect is added with a large amount of nano carbon materials; it is well known that nanocarbon materials are expensive, resulting in higher costs for soil treatment.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nano carbon composite material with a soil remediation function; the nano carbon composite material with the soil remediation function adopts sewage treatment to recover carbon materials, reasonably utilizes waste materials after sewage treatment, and reduces the raw material cost to a certain extent; meanwhile, the nano carbon composite material has excellent heavy metal restoration capability.
The technical problem to be solved by the invention is realized by the following technical scheme:
a nano carbon composite material with a soil remediation function comprises the following components in parts by weight:
50-70 parts of diatomite; 20-30 parts of carbon materials are recovered in sewage treatment; 5-10 parts of carbon nanotubes; 5-10 parts of calcium hydroxide.
Preferably, the nanocarbon composite material with the soil remediation function comprises the following components in parts by weight:
60-70 parts of diatomite; 25-30 parts of carbon material is recovered in sewage treatment; 8-10 parts of carbon nanotubes; 8-10 parts of calcium hydroxide.
Preferably, the nanocarbon composite material with the soil remediation function comprises the following components in parts by weight:
60 parts of diatomite; 25 parts of carbon material is recovered by sewage treatment; 8 parts of carbon nano tubes; and 8 parts of calcium hydroxide.
Preferably, the carbon material recovered by sewage treatment is a carbon material recovered after the carbon material is used for sewage treatment.
Preferably, the sewage is high-density aquaculture sewage.
Preferably, the carbon material is prepared by the following method:
(1) mixing bentonite and sepiolite, soaking in concentrated acid for 8-15 h, and washing with water to be neutral to obtain a bentonite-sepiolite mixture;
(2) mixing oil with melamine, trehalose and a surfactant to obtain an oil mixture;
(3) adding a bentonite-sepiolite mixture and an oil mixture into an organic solvent, uniformly stirring, and concentrating to remove the organic solvent to obtain the bentonite-sepiolite-oil mixture;
(4) placing the bentonite-sepiolite-grease mixture under the protection of nitrogen; heating to 400-500 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 1-2 h, heating to 900-1100 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2-3 h, cooling, washing and drying the product to obtain the high-density aquaculture sewage purification material.
Further preferably, the mass usage ratio of the bentonite to the sepiolite in the step (1) is 1-3: 1-3; in the step (2), the mass and dosage ratio of the grease to the melamine, the trehalose and the surfactant is 20-30: 3-5: 3-5: 1-3; in the step (3), the dosage ratio of the organic solvent, the bentonite-sepiolite mixture and the grease mixture is 20-30 mL: 1-3 g: 1-3 g.
Preferably, the carbon material is viscose-based activated carbon fiber recovered after the viscose-based activated carbon fiber is used for sewage treatment.
The invention also provides a soil improvement method, which comprises the following steps: adding the nanocarbon composite material as claimed in any one of claims 1 to 7 into soil to be restored, uniformly mixing, adding water, and standing for 30-60 days to obtain improved soil.
Preferably, the dosage of the nano carbon composite material is 0.1-1% of the mass of the soil.
Preferably, water is added to maintain the water content of the soil at 20-30%.
Has the advantages that: the invention provides a brand-new nano carbon composite material with a soil remediation function, wherein the nano carbon composite material adopts a sewage treatment recycled carbon material to replace part of carbon nanotube materials, so that the soil remediation cost is reduced; the inventor researches and discovers that the carbon material recovered by sewage treatment and used in combination with the carbon nano tube has excellent heavy metal removal capability; especially lead and cadmium removal. In addition, the carbon material is recovered in the sewage treatment, so that the components in the aquaculture sewage are adsorbed, and the fertility of the soil can be increased when the carbon material is used in the soil.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1 preparation of nanocarbon composite material having soil remediation function
Weighing 60 parts of diatomite, 25 parts of a sewage treatment recycled carbon material, 8 parts of carbon nano tubes and 8 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
The carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating high-density aquaculture sewage; the carbon material is prepared by the following method:
(1) mixing bentonite and sepiolite according to a mass ratio of 1: 1, mixing, soaking in concentrated nitric acid for 12 hours, and then washing with water to be neutral to obtain a bentonite-sepiolite mixture;
(2) mixing oil (tung oil is selected), melamine, trehalose and a surfactant (ethanol lauryl sodium sulfosuccinate monoester disodium) according to a mass ratio of 25: 4: 4: 2, mixing to obtain a grease mixture;
(3) adding bentonite-sepiolite mixture and oil mixture into organic solvent (ethanol), stirring, concentrating, and removing organic solvent to obtain bentonite-sepiolite-oil mixture; wherein the dosage ratio of the organic solvent, the bentonite-sepiolite mixture and the grease mixture is 25 mL: 1 g: 1g of a compound;
(4) placing the bentonite-sepiolite-grease mixture under the protection of nitrogen; heating to 450 ℃ at the heating rate of 4 ℃/min, preserving heat for 1.5h, heating to 1000 ℃ at the heating rate of 4 ℃/min, preserving heat for 2.5h, cooling, washing the product (firstly washing with 1mol/L hydrochloric acid, then washing with water), and drying to obtain the carbon material.
Example 2 preparation of nanocarbon composite Material having soil remediation function
Weighing 50 parts of diatomite, 30 parts of a sewage treatment recovery carbon material, 10 parts of carbon nano tubes and 5 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
The carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating high-density aquaculture sewage; the carbon material was prepared in the same manner as in example 1.
Example 3 preparation of nanocarbon composite Material having soil remediation function
Weighing 70 parts of diatomite, 20 parts of a sewage treatment recovery carbon material, 5 parts of carbon nano tubes and 10 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
The carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating high-density aquaculture sewage; the carbon material was prepared in the same manner as in example 1.
Comparative example 1 preparation of nanocarbon composite material having soil remediation function
Weighing 60 parts of diatomite, 33 parts of a sewage treatment recycled carbon material and 8 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
The carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating high-density aquaculture sewage; the carbon material was prepared in the same manner as in example 1.
Comparative example 1 is different from example 1 in that only the carbon material is recovered by sewage treatment without using carbon nanotubes.
Comparative example 2 preparation of nanocarbon composite material having soil remediation function
And weighing 60 parts of diatomite, 33 parts of carbon nano tube and 8 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
Comparative example 2 differs from example 1 in that only carbon nanotubes are used and no wastewater treatment is used to recover carbon material.
Comparative example 3 preparation of nanocarbon composite material having soil remediation function
Weighing 60 parts of diatomite, 25 parts of a sewage treatment recycled carbon material, 8 parts of carbon nano tubes and 8 parts of calcium hydroxide according to the parts by weight, and uniformly mixing to obtain the nano carbon composite material with the soil remediation function.
The carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating high-density aquaculture sewage; the carbon material is graphene.
Example 4 soil improvement method
(1) Ploughing the soil to be improved;
(2) adding a nano carbon composite material with a soil remediation function (the using amount is 0.5 percent of the soil mass) into the soil to be ploughed, and uniformly mixing;
(3) watering in soil, keeping soil humidity at 25%, and standing for 45 days to obtain improved soil.
Test examples
Digging soil in the soil polluted by Pb and Cd, dividing the soil into 5 parts, and putting the 5 parts into a planting box; wherein 1 part of the nano carbon composite material is not subjected to any treatment, and the other 4 parts of the nano carbon composite material with the soil remediation function, which is prepared in the example 1 and the comparative examples 1 to 3, are respectively remediated according to the method of the example 4. After the repair is finished, spinach is planted on 5 parts of soil according to a conventional method; after the spinach is ripe, taking 20 spinach in each part to detect Pb and Cd in the spinach, and taking an average value; the specific test results are shown in Table 1.
TABLE 1 detection results of Pb and Cd in spinach
| Repair material | Average Pb content (mg/kg) | Average Cd content (mg/kg) |
| Example 1 nanocarbon composite | 0.054 | 0.081 |
| Comparative example 1 nanocarbon composite | 0.14 | 0.17 |
| Comparative example 2 nanocarbon composite | 0.11 | 0.13 |
| Comparative example 3 nanocarbon composite | 0.13 | 0.15 |
| Without adding repairing material | 0.28 | 0.35 |
From the data, the contents of Pb and Cd in the spinach planted on the soil repaired by the nanocarbon composite material with the soil repairing function prepared in the embodiment 1 are obviously lower than those of the unrepaired soil; this shows that the nanocarbon composite material with a soil remediation function prepared in example 1 has a significant capacity of remedying heavy metals of Pb and Cd in soil.
As can be seen from the repair data of comparative examples 1 and 2, although the repair data is improved, the repair capability of the nano carbon composite material is far inferior to that of the nano carbon composite material with the soil repair function prepared in example 1. The method shows that the restoring capability of the carbon material and the carbon nano tube to heavy metals is mutually promoted and mutually cooperated after the carbon material and the carbon nano tube are mixed by adopting sewage treatment in the nano carbon composite material; the restoring capability of the composite material to heavy metal is far greater than that of carbon material or carbon nano tube recovered by sewage treatment alone.
As can be seen from the repair data of comparative example 3, although the repair data is improved, the repair capability is far inferior to that of the nanocarbon composite material with the soil repair function prepared in example 1. The carbon material prepared by the method can generate the capability of synergistically repairing the heavy metal with the carbon nano tube, and other carbon materials and the carbon nano tube cannot generate the capability of synergistically repairing the heavy metal.
Claims (8)
1. The nano carbon composite material with the soil remediation function is characterized by comprising the following components in parts by weight:
50-70 parts of diatomite; 20-30 parts of carbon materials are recovered in sewage treatment; 5-10 parts of carbon nanotubes; 5-10 parts of calcium hydroxide;
the carbon material recovered by sewage treatment refers to the carbon material recovered after the carbon material is used for treating sewage;
the carbon material is prepared by the following method:
(1) mixing bentonite and sepiolite, soaking in concentrated acid for 8-15 h, and washing with water to be neutral to obtain a bentonite-sepiolite mixture;
(2) mixing oil with melamine, trehalose and a surfactant to obtain an oil mixture;
(3) adding a bentonite-sepiolite mixture and an oil mixture into an organic solvent, uniformly stirring, and concentrating to remove the organic solvent to obtain the bentonite-sepiolite-oil mixture;
(4) placing the bentonite-sepiolite-grease mixture under the protection of nitrogen; heating to 400-500 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 1-2 h, heating to 900-1100 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2-3 h, cooling, washing and drying the product to obtain the carbon material.
2. The nanocarbon composite material with a soil remediation function according to claim 1, comprising the following components in parts by weight:
60-70 parts of diatomite; 25-30 parts of carbon material is recovered in sewage treatment; 8-10 parts of carbon nanotubes; 8-10 parts of calcium hydroxide.
3. The nanocarbon composite material with a soil remediation function according to claim 1, comprising the following components in parts by weight:
60 parts of diatomite; 25 parts of carbon material is recovered by sewage treatment; 8 parts of carbon nano tubes; and 8 parts of calcium hydroxide.
4. The nanocarbon composite material having a soil remediation function of claim 1, wherein the wastewater is high-density aquaculture wastewater.
5. The nanocarbon composite material with the soil remediation function as claimed in claim 1, wherein the mass usage ratio of the bentonite to the sepiolite in the step (1) is 1-3: 1-3; in the step (2), the mass and dosage ratio of the grease to the melamine, the trehalose and the surfactant is 20-30: 3-5: 3-5: 1-3; in the step (3), the dosage ratio of the organic solvent, the bentonite-sepiolite mixture and the grease mixture is 20-30 mL: 1-3 g: 1-3 g.
6. The nanocarbon composite material having a soil remediation function as claimed in claim 1, wherein the carbon material is a viscose-based activated carbon fiber recovered from a sewage treatment process using the viscose-based activated carbon fiber.
7. A method of soil improvement comprising the steps of: adding the nanocarbon composite material as claimed in any one of claims 1 to 6 into soil to be restored, uniformly mixing, adding water, and standing for 30-60 days to obtain improved soil.
8. The soil improvement method according to claim 7, wherein the amount of the nanocarbon combination material is 0.1-1% of the mass of the soil; adding water to keep the water content of the soil at 20-30%.
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Patent Citations (5)
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| CN104927870A (en) * | 2015-06-05 | 2015-09-23 | 中国地质科学院矿产资源研究所 | Novel material for repairing heavy metal Cr-Pb-Cd polluted soil, and preparation method and application method thereof |
| CN107099300A (en) * | 2017-06-09 | 2017-08-29 | 山东科技大学 | A kind of soil-repairing agent, its preparation method and its application |
| CN108624327A (en) * | 2018-02-07 | 2018-10-09 | 浙江海逸环科院有限公司 | A kind of soil-repairing agent and preparation method thereof |
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