CN112239671A - Passivator for arsenic and cadmium compound polluted farmland and use method thereof - Google Patents
Passivator for arsenic and cadmium compound polluted farmland and use method thereof Download PDFInfo
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- CN112239671A CN112239671A CN201910642881.XA CN201910642881A CN112239671A CN 112239671 A CN112239671 A CN 112239671A CN 201910642881 A CN201910642881 A CN 201910642881A CN 112239671 A CN112239671 A CN 112239671A
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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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
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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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- 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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- Engineering & Computer Science (AREA)
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- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention discloses a passivating agent for arsenic and cadmium compound polluted farmland and a preparation method thereof, wherein the passivating agent comprises the following raw materials in percentage by mass: 15-40% of sepiolite, 5-10% of sodium diethyldithiocarbamate, 15-30% of attapulgite, 3-10% of quicklime, 15-35% of biochar and 10-25% of ferric sulfate; the preparation method comprises the following steps: adding sepiolite into sodium diethyldithiocarbamate solution, grinding and drying, mixing with attapulgite, quicklime, biochar and ferric sulfate, and carrying out disc granulation to obtain the passivator. The environment-friendly passivator has the advantages of high efficiency of repairing farmlands polluted by heavy metals such as arsenic and cadmium, low repairing cost, easily available raw material components, simple preparation method, no dust generated in the application process, no harm to the health of operators, no air pollution, no hardening of soil after long-term use, and capability of simultaneously repairing farmlands polluted by various heavy metals.
Description
Technical Field
The invention relates to the field of heavy metal contaminated soil remediation, in particular to a passivator for in-situ remediation of an arsenic and cadmium combined contaminated farmland.
Background
With the development of society, the discharge of three wastes in industrial production, the use of a large amount of chemical fertilizers and pesticides in agricultural production, atmospheric sedimentation and other approaches cause a large amount of heavy metals to enter the agricultural field, thereby not only affecting the quality of cultivated land and agricultural products, but also entering human bodies through food chains to accumulate in the human bodies and endanger the health of the human bodies. In 2014, the national environmental protection ministry and the national soil resources ministry of national soil pollution situation survey bulletin show that the exceeding rate of total pollutants in national soil is 16.1%, the national soil environment situation is overall not optimistic, and the quality of the cultivated land soil environment is great. The pollution problems of arsenic, cadmium and the like in the inorganic pollution are more prominent. In polluted soil, the pollution is often combined pollution of various heavy metals.
At present, the approaches for treating the heavy metal contaminated soil are mainly 2, and firstly, the total amount of heavy metals in the soil is reduced (engineering measures, phytoremediation and the like); the other is to change the existing form of heavy metal in soil and reduce the migration and bioavailability (chemical inactivation and microbial remediation) of heavy metal in the environment. The engineering measure cost is high, the problems of secondary pollution risk and the like exist in the farmland, the phytoremediation period is long, the follow-up plant treatment is difficult, and the practical application is limited. Therefore, for farmland heavy metal contaminated soil, the method has important significance for reducing the content of effective heavy metals in the soil by a passivator in-situ remediation technology and ensuring the safe production of crops. In addition, the heavy metal pollution of farmlands in China has the characteristics of large area and medium-light pollution as main characteristics, and the in-situ passivation restoration technology is widely concerned due to simple operation, quick response and suitability for large-area pollution treatment.
Chinese patent document CN105754610A discloses a heavy metal cadmium and arsenic composite contaminated soil passivator and a preparation method thereof. The raw materials of the passivator comprise biomass charcoal (30-50%), diatomite (5-10%), sodium bentonite (5-10%), activated alumina (5-10%), dithiocarbamate (10-20%), ethylenediamine tetraacetic acid (5-10%), tartaric acid (5-10%), polyacrylamide (5-10%) and sodium dodecyl sulfate (5-10%). The preparation method comprises the following steps: uniformly stirring biomass charcoal, diatomite, sodium bentonite, activated alumina, ethylenediamine tetraacetic acid, tartaric acid, polyacrylamide and sodium dodecyl sulfate according to corresponding mass proportions to form a mixture, adding dithiocarbamate according to corresponding mass proportions into the mixture optimized in the step (1), and sufficiently and uniformly stirring to obtain the prepared soil passivator. The product of the patent can well repair heavy metals such as arsenic, cadmium and the like in farmlands, but the raw materials of the product are complex, the product is powdery, and certain environmental protection problems exist in the storage and use processes.
Chinese patent document CN104031651A discloses a passivation modifier for heavy metal contaminated farmlands and a use method thereof, wherein the passivation modifier is prepared from nano iron powder, fly ash, zeolite, calcium magnesium phosphate fertilizer, medical stone, hydroxypropyl modified SiO 2/chitosan nano particles and pore spherical cellulose according to the weight ratio of 10-25: 15-40: 25-50: 1-10: 5-15: 10-20. The composite passivator can be well applied to composite contaminated soil, but the possibility of heavy metal pollution exists when the fly ash is not properly selected.
Therefore, the development of the passivator which is low in cost, easy in raw material obtaining, high in efficiency and environment-friendly is of great significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the passivator capable of repairing the farmland polluted by arsenic and cadmium and effectively reducing the absorption of agricultural products to arsenic and cadmium.
In the present specification, unless otherwise specified, "content" means mass percentage.
In order to achieve the purpose, the invention adopts the technical scheme that: an arsenic and cadmium composite pollution farmland passivator comprises the following raw materials in percentage by mass: 15-40% of sepiolite, 5-10% of sodium diethyldithiocarbamate, 15-30% of attapulgite, 3-10% of quicklime, 15-35% of biochar and 10-25% of ferric sulfate.
Preferably, the sepiolite is a dry powder with a particle size of 50-200 mesh, wherein the content of magnesium oxide is more than 20%.
Preferably, the attapulgite is a dry powder with a particle size of 50-200 meshes, wherein the content of aluminum oxide is required to be more than 8%, the content of ferric oxide is required to be more than 4%, and the content of magnesium oxide is required to be more than 8%.
Preferably, the sodium diethyldithiocarbamate is a solution with the mass concentration of 500-800 mg/L.
Preferably, the quicklime is a 50-200 mesh dry powder with a calcium oxide content of greater than 95%.
Preferably, the biochar is obtained by crushing crop straws into powder, sieving the powder with a 50-200-mesh sieve, drying and carbonizing the powder.
The crops can be wheat, rice, corn, rape, sorghum, etc.
Preferably, the iron sulfate is a dry powder with a particle size of 50-200 mesh.
The invention also aims to provide a preparation method of the passivator for repairing the farmland compositely polluted by arsenic and cadmium, which comprises the following steps:
adding sepiolite into the sodium diethyldithiocarbamate solution prepared according to the proportion, fully stirring for 2h, filtering, drying, grinding, screening by a 50-200 mesh sieve to obtain a first raw material.
And uniformly mixing the first raw material, attapulgite, quicklime and biochar according to the proportion to obtain a second raw material.
Adding ferric sulfate into the second raw material, and fully and uniformly mixing.
And transferring the uniformly mixed materials into a disc through a feeding tank, and preparing particles by using a disc granulation method to obtain the passivator for repairing the arsenic and cadmium composite polluted farmland.
Preferably, the particle size of the passivator particles is 2-5 mm.
The passivating agent is applied to the treatment of the farmland with arsenic and cadmium combined pollution.
Preferably, the dosage of the farmland passivating agent is 200-400 kg/mu.
Compared with the prior art, the invention has the following advantages:
firstly, the farmland soil passivator disclosed by the invention adopts composite repairing effects of adsorption, ion exchange, chelation, coagulating sedimentation, nutrition balance and the like to enable heavy metals such as arsenic, cadmium and the like in soil to form stable chemical forms, and the migration and diffusion capacity of the heavy metals in the soil is reduced, so that the environmental risk is reduced, the enrichment amount of heavy metals by agricultural action is reduced, and the safe use of a farmland is realized. The environment-friendly passivator has the advantages of high efficiency of repairing farmlands polluted by heavy metals such as arsenic and cadmium, low repairing cost, easily available raw material components, simple preparation method, no dust generated in the application process, no harm to the health of operators, no air pollution, no hardening of soil after long-term use, and capability of simultaneously repairing farmlands polluted by various heavy metals.
Secondly, during the enclosing period of the invention by adding water, ferric sulfate in the passivating agent is released and is quickly dissolved in water to form a large amount of iron-containing complexes in the soil solution, and the iron-containing complexes can form flocculent coagulants with colloidal particles in the soil solution through a certain action to generate a coagulating sedimentation effect and precipitate hydroxide of cadmium; simultaneously can react with heavy metal arsenic to produce FeAsO3And FeAsO4. The produced iron arsenic compound sediment is deposited by the hydrolysate of the iron salt through coagulating sedimentation. Sepiolite is a natural hydrated magnesium silicate clay mineral composed of silicon-oxygen tetrahedron and magnesium oxide octahedron. The structure provides a large number of channels and holes, and exchangeable cations have obvious passivation effect on heavy metal cadmium. After the sepiolite is modified by a heavy metal trapping agent of sodium diethyldithiocarbamate, the repairing capability of the heavy metal in the stabilized soil is obviously improved through synergistic effects of chelation, adsorption, coagulating sedimentation and the like, and the consumption of a passivating agent is reduced.
Thirdly, the attapulgite clay used in the invention is a water-containing magnesium-rich aluminosilicate clay mineral which takes attapulgite as a main component and has a chain layer structure, has larger specific surface area, cation exchange capacity and adsorption performance, and has certain repair capacity for arsenic and cadmium in soil. In addition, the attapulgite can be used as a binder, and can well form granulation conditions.
And fourthly, the biochar in the passivator component is rich in carbon and certain ash content, wherein the ash is mainly alkaline, has a huge specific surface area and a developed porous loose structure, is rich in surface functional groups, and can increase passivation on heavy metals by increasing the pH value of a medium.
In addition, the biochar can prevent farmland soil hardening caused by long-term use of lime. No secondary pollution is caused. The passivator can also be used for repairing heavy metal contaminated soil of mines and contaminated soil of industrial sites.
Detailed Description
Embodiments of the present invention will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein are within the scope of the present invention.
In the following embodiments, the sepiolite, the attapulgite, the quicklime, the biochar and the ferric sulfate are all powder, wherein the content of magnesium oxide in the sepiolite is more than 20 percent, and the content of calcium oxide in the quicklime is more than 95 percent.
Preparation example 1:
the passivator for cadmium and arsenic compound polluted farmland is prepared according to the following steps:
(1) adding sepiolite (25%) into a sodium diethyldithiocarbamate (5%) solution, fully stirring for 2h, filtering, drying, grinding, and screening by a 50-200 mesh sieve to obtain a first raw material; (2) uniformly mixing the obtained first raw material with attapulgite (20%), quicklime (5%) and biochar (30%) to obtain a second raw material; (3) adding ferric sulfate (15%) into the second raw material, and fully and uniformly mixing to obtain a third raw material; (4) transferring the obtained third raw material into a disc through a feeding tank, and preparing particles by using a disc granulation method to obtain the passivator for repairing the arsenic and cadmium composite polluted farmland.
Preparation example 2:
a passivator for cadmium and arsenic compound polluted farmland is prepared in the same way as in preparation example 1, except that the proportion of each component is as follows: sepiolite (25%), sodium diethyldithiocarbamate (0%), attapulgite (25%), quicklime (5%), biochar (30%) and ferric sulfate (15%).
Preparation example 3:
a passivator for cadmium and arsenic compound polluted farmland is prepared in the same way as in preparation example 1, except that the proportion of each component is as follows: sepiolite (30%), sodium diethyldithiocarbamate (5%), attapulgite (25%), quicklime (5%), biochar (30%), ferric sulfate (5%).
The particle diameter of the passivator is 2-5 mm.
The passivator is applied to the treatment of arsenic and cadmium combined pollution farmland, and specifically comprises the following steps:
(1) applying a passivating agent: uniformly spreading the granular passivator on the surface of a farmland 10 days before sowing or transplanting crops;
(2) deep ploughing: deeply loosening 30cm of farmland soil by using a subsoiler;
(3) rotary tillage: rotary tillage is carried out for 2 times by using a rotary cultivator, and the rotary tillage depth is 20 cm;
(4) adding water and standing: watering to saturation, and standing for 5 days.
And (3) carrying out a wheat field plot repairing test in a farmland which is polluted by cadmium and arsenic in Tianshui city of Gansu province. Dividing the field into 18 cells in total, randomly arranging at a line spacing of 15cm, and making the cell size 5m × 4m (20 m)2) The farmland is divided by ridges with the height of 30cm and the width of 30cm, agricultural films are laid on the ridges, independent irrigation ditches are arranged in each region, and 5 rows of wheat are arranged around the field as protection rows to eliminate marginal effects. Each example was repeated 3 times, i.e., each example was assigned 3 hoursThe values calculated in table 1 below are thus each an average of 3 cells.
After the passivator is applied, compound fertilizer is applied as base fertilizer before sowing, the application amount is 30 kg/mu, and other topdressing, watering, disinsection and the like are carried out according to the conventional operation of the field.
Example 1:
the passivator prepared in preparation example 1 is applied, and the dosage is 400 kg/mu.
Example 2:
the passivator prepared in preparation example 2 is applied, and the dosage is 400 kg/mu.
Example 3:
the passivator prepared in preparation example 3 is applied, and the dosage is 400 kg/mu.
Example 4 (control):
according to the local conventional seed method, no passivator is applied.
Example 5:
the passivator prepared in preparation example 1 is applied at the dosage of 200 kg/mu.
Example 6:
the passivator prepared in preparation example 1 is applied at the dosage of 300 kg/mu.
Experimental example:
the method comprises the steps of respectively collecting samples of all the subareas by a plum blossom-shaped sampling method, namely selecting 5 points for each processing district, and collecting 10 wheat plants nearby each point, wherein 50 wheat plants are counted in each district. Separating wheat grains, deactivating enzyme at 105 deg.C for 30min, oven drying at 70 deg.C to constant mass, measuring dry mass, and pulverizing the dried sample and sieving with 40 mesh sieve. The total amount of Cd and As in the wheat grain sample is determined by dry ash digestion (GB/T5009-2010).
In Table 1, the respective reduction rates of examples 1-3 and examples 5-6 were calculated from the reduction rates of the respective measured values with respect to the measured value of the control (i.e., example 4). As can be seen from Table 1, in examples 1-3 and examples 5-6, the applied passivates prepared by the invention can achieve at least 49.12% of Cd reduction rate and at least 73.19% of As reduction rate. In particular, in the case of example 1, the passivating agent of the invention reduced Cd by 75.66%, in the case of example 2, the passivating agent of the invention reduced As by 88.80%. Therefore, the passivating agent has better passivating effect on heavy metal cadmium and arsenic.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
TABLE 1 EXAMPLES 1-6 reduction of total Cd, As in soil
| Examples | Total Cd (mg/kg) | Percentage of reduction (%) | As (mg/kg) | Percentage of reduction (%) |
| Example 1 | 0.055 | 75.66 | 0.078 | 87.48 |
| Example 2 | 0.106 | 53.10 | 0.071 | 88.80 |
| Example 3 | 0.113 | 50.00 | 0.167 | 73.19 |
| Example 4 (control) | 0.226 | -- | 0.623 | -- |
| Example 5 | 0.115 | 49.12 | 0.128 | 79.45 |
| Example 6 | 0.072 | 68.14 | 0.091 | 85.39 |
Claims (10)
1. The passivator for the arsenic and cadmium compound polluted farmland is characterized by comprising the following raw materials in percentage by mass: 15-40% of sepiolite, 5-10% of sodium diethyldithiocarbamate, 15-30% of attapulgite, 3-10% of quicklime, 15-35% of biochar and 10-25% of ferric sulfate.
2. The passivating agent according to claim 1, wherein the sepiolite is a dry powder with a particle size of 50-200 mesh, wherein the content of magnesium oxide is greater than 20%.
3. The passivator as claimed in claim 1 wherein the attapulgite is a 50-200 mesh dry powder with an alumina content greater than 8%, an iron oxide content greater than 4% and a magnesium oxide content greater than 8%.
4. The passivating agent as claimed in claim 1, wherein the sodium diethyldithiocarbamate is a solution with a mass concentration of 500-800 mg/L.
5. The passivator of claim 1 wherein the quicklime is a 50-200 mesh particle size dry powder with a calcium oxide content of greater than 95%.
6. The passivator of claim 1 wherein the biochar is obtained by crushing crop straws into powder, sieving the powder with a 50-200 mesh sieve, drying and carbonizing the powder.
7. The passivating agent according to claim 1, wherein the iron sulfate is a dry powder with a particle size of 50-200 mesh.
8. The preparation method of the arsenic and cadmium polluted farmland passivating agent as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) adding sepiolite into the sodium diethyldithiocarbamate solution prepared according to the proportion, fully stirring for 2h, filtering, drying, grinding, and screening by a 50-200 mesh sieve to obtain a first raw material;
(2) uniformly mixing the first raw material, attapulgite, quicklime and biochar according to the proportion to obtain a second raw material;
(3) adding ferric sulfate into the second raw material, and fully and uniformly mixing to obtain a third raw material;
(4) and transferring the third raw material into a disc through a feeding tank, and preparing particles by using a disc granulation method to obtain the passivator for repairing the arsenic and cadmium composite polluted farmland.
9. The method according to claim 8, wherein the particle size of the passivating agent is 2-5 mm.
10. The passivator of claim 1, applied to control of farmland polluted by arsenic and cadmium.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939696A (en) * | 2021-02-28 | 2021-06-11 | 湖南中米环保科技有限公司 | Soil conditioner for treating farmland cadmium and arsenic combined pollution and application method thereof |
| CN113632614A (en) * | 2021-08-13 | 2021-11-12 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| CN114133931A (en) * | 2021-10-28 | 2022-03-04 | 中冶南方都市环保工程技术股份有限公司 | Repairing agent for heavy metal polluted clay and preparation method and application thereof |
| CN114289490A (en) * | 2021-12-21 | 2022-04-08 | 江苏隆昌化工有限公司 | Carbon-fixing material for repairing heavy metal polluted farmland |
| CN115404081A (en) * | 2022-07-29 | 2022-11-29 | 广西壮族自治区环境保护科学研究院 | Passivator for repairing heavy metal lead, zinc and arsenic combined pollution and application |
| WO2023019787A1 (en) * | 2021-08-16 | 2023-02-23 | 江苏隆昌化工有限公司 | Ultra-stable mineralized soil remediation material for farmland contaminated by heavy metals |
| CN117063655A (en) * | 2023-08-15 | 2023-11-17 | 湖南省土壤肥料研究所 | Method for preventing and controlling rice field submerged cultivation and cooperatively reducing cadmium in water flooding environment |
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2019
- 2019-07-17 CN CN201910642881.XA patent/CN112239671A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939696A (en) * | 2021-02-28 | 2021-06-11 | 湖南中米环保科技有限公司 | Soil conditioner for treating farmland cadmium and arsenic combined pollution and application method thereof |
| CN113632614A (en) * | 2021-08-13 | 2021-11-12 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| CN113632614B (en) * | 2021-08-13 | 2022-08-16 | 金华生物质产业科技研究院 | Preparation and application methods of compound heavy metal contaminated soil remediation material |
| WO2023019787A1 (en) * | 2021-08-16 | 2023-02-23 | 江苏隆昌化工有限公司 | Ultra-stable mineralized soil remediation material for farmland contaminated by heavy metals |
| CN114133931A (en) * | 2021-10-28 | 2022-03-04 | 中冶南方都市环保工程技术股份有限公司 | Repairing agent for heavy metal polluted clay and preparation method and application thereof |
| CN114289490A (en) * | 2021-12-21 | 2022-04-08 | 江苏隆昌化工有限公司 | Carbon-fixing material for repairing heavy metal polluted farmland |
| CN115404081A (en) * | 2022-07-29 | 2022-11-29 | 广西壮族自治区环境保护科学研究院 | Passivator for repairing heavy metal lead, zinc and arsenic combined pollution and application |
| CN117063655A (en) * | 2023-08-15 | 2023-11-17 | 湖南省土壤肥料研究所 | Method for preventing and controlling rice field submerged cultivation and cooperatively reducing cadmium in water flooding environment |
| CN117063655B (en) * | 2023-08-15 | 2024-04-23 | 湖南省土壤肥料研究所 | Method for preventing and controlling rice field submerged cultivation and cooperatively reducing cadmium in water flooding environment |
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Application publication date: 20210119 |