CN112724984A - Cadmium-polluted agricultural land soil composite conditioner and use method thereof - Google Patents
Cadmium-polluted agricultural land soil composite conditioner and use method thereof Download PDFInfo
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- CN112724984A CN112724984A CN202110063553.1A CN202110063553A CN112724984A CN 112724984 A CN112724984 A CN 112724984A CN 202110063553 A CN202110063553 A CN 202110063553A CN 112724984 A CN112724984 A CN 112724984A
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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
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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
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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
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- C09K2101/00—Agricultural use
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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Abstract
The invention relates to a cadmium-polluted agricultural land soil composite conditioner and a using method thereof, belonging to the technical field of heavy metal-polluted soil remediation. The composite conditioner comprises the following components in percentage by mass: 25-50% of DTPA modified biochar, 30-60% of adsorbent and 10-40% of precipitator. According to the invention, the action units are integrated to form a combined synergistic treatment mechanism of 'chelation-adsorption-precipitation', and the dosage proportion of the action units is further optimized, so that the treatment effect of the composite conditioner is finally improved. The composite conditioner has the characteristics of small dosage of a single medicament, no secondary pollution, capability of effectively reducing the content of available cadmium in soil on the premise of lower addition amount, good long-term stability and the like.
Description
Technical Field
The invention belongs to the technical field of heavy metal contaminated soil remediation, and particularly relates to a cadmium contaminated soil composite conditioner for agricultural land and a using method thereof.
Background
The soil condition of cultivated land in China is not optimistic, the total exceeding rate of soil in China reaches 16.1%, the proportion of heavy pollution points accounts for 1.1%, and the area is about 1980 ten thousand mu. According to the national soil pollution condition survey bulletin (2014), the over-standard rates of 8 inorganic pollution point sites of cadmium, mercury, arsenic, copper, lead, chromium, zinc and nickel in the national soil are respectively 7%, 1.6%, 2.7%, 2.1%, 1.5%, 1.1%, 0.9% and 4.8%, and the over-standard rate of cadmium in the soil is the highest.
Cadmium pollution to cultivated land is mainly from waste water, waste gas and waste residues generated in mining, metal smelting and industrial production. After the cultivated land is polluted by cadmium, the cadmium can enter the human body through the food chain and is gathered in the human body, and chronic poisoning is caused. Cadmium forms cadmium sulfur protein in human body, and selectively accumulates in liver and kidney. Among them, the kidney can absorb cadmium which enters nearly 1/3 in vivo, and is the 'target organ' of cadmium poisoning. Diabetes, proteinuria and aminouria develop in patients due to cadmium damage to renal tubules. The metabolism of the skeleton is blocked, and a series of symptoms such as osteoporosis, atrophy, deformation and the like are caused.
The passivant is applied to the cadmium-polluted cultivated land, so that the migration activity and the bioavailability of cadmium can be reduced, and the absorption of cadmium by crops is blocked, thereby ensuring the grain safety. The technology has the advantages of quick effect, simple operation, no influence on crop planting, low repair and treatment cost and the like, and has been widely researched and used. However, the existing passivators are poor in passivation effect, most passivators are only suitable for medium-light cadmium polluted soil, and the treatment of the heavily polluted soil is often combined with other technologies, such as measures of low-accumulation crop replacement planting, water and fertilizer management, leaf surface resistance control and the like, so that the operation difficulty and the treatment cost are greatly increased. Lime is the most widely used passivator for cadmium-polluted cultivated land, but the problems of seedling burning, soil hardening and the like are easily caused when the lime consumption exceeds about 3 per mill of the soil quality of a cultivated layer, and the normal growth of crops is influenced. How to improve the passivation effect of the passivator and reduce the dosage of a single medicament is an urgent problem to be solved.
Disclosure of Invention
In view of the above, one of the objectives of the present invention is to provide a composite conditioner for soil polluted by cadmium; the other purpose is to provide a use method of the cadmium-polluted agricultural land soil composite conditioner.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the cadmium-polluted agricultural land soil composite conditioner comprises the following components in percentage by mass: 25-50% of DTPA modified biochar, 30-60% of adsorbent and 10-40% of precipitator.
Preferably, the DTPA modified biochar is prepared by the following method: dissolving DTPA in water of 45-95 deg.C, adding biochar, stirring at 45-95 deg.C for 0.5-5h, cooling to room temperature, vacuum filtering, oven drying, grinding, and sieving.
Preferably, the mass ratio of the DTPA to the biochar to the water is 1:2-10: 40-100.
Preferably, the biochar is one of corn biochar, rice hull biochar or straw biochar.
Preferably, the drying specifically comprises: drying at 35-55 deg.C for 24-72 h.
Preferably, the size of the sieve mesh during sieving is 10-100 meshes.
Preferably, the adsorbent is one or more of bentonite, zeolite, humic acid or sodium humate.
Preferably, the precipitator is one of calcium hydroxide, calcium oxide, calcium carbonate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride or iron powder.
2. The application method of the cadmium-polluted agricultural land soil composite conditioner comprises the following steps: adding 4-20% of the cadmium-polluted agricultural land soil by the amount of the composite conditioner, adding water into the composite conditioner and the cadmium-polluted agricultural land soil, uniformly mixing, and standing for more than 14 days under natural conditions.
The invention has the beneficial effects that: the invention provides a cadmium-polluted agricultural land soil composite conditioner and a use method thereof, the composite conditioner consists of DTPA modified biochar, an adsorbent and a precipitator, by carrying out centralized coordination on each action unit, a combined synergistic treatment mechanism of 'chelation-adsorption-precipitation' is formed, and further optimizes the dosage and proportion of each action unit to achieve the optimal synergistic effect with each other, so that the adsorbent adsorbs water-soluble cadmium in the soil, meanwhile, the DTPA modified biochar is used for chelating the rest effective cadmium in the soil, and the effective cadmium is enriched after being adsorbed and chelated, so that the contact chance of the effective cadmium and a precipitator can be increased, the cadmium-containing composite conditioner has precipitation/coprecipitation reaction with a precipitator, the passivation effect on cadmium is enhanced, the dosage ratio of the three is strictly controlled, the complete adsorption and precipitation of effective cadmium is ensured, and the treatment effect of the composite conditioner is finally improved. The DTPA modified biochar has the efficient chelating capacity of DTPA to cadmium, the adsorption performance and the pH adjusting capacity of biochar, the migration capacity and the bioavailability of heavy metal cations such as cadmium in soil can be effectively reduced, the absorption of crops to the heavy metal cations such as cadmium is reduced, in addition, in the process of preparing the DTPA modified biochar, the DTPA is dissolved in hot water and enters a biochar pore passage through mechanical stirring by further optimizing the modification temperature, the modification time and the mass ratio of raw materials, the DTPA is cooled after the modification is finished, the DTPA is retained in the biochar pore passage, and the DTPA and the biological pore passage are tightly combined to ensure that the finally prepared DTPA modified biochar can fully realize the functions. The molecular structure of the adsorbent contains a large amount of oxygen-containing active functional groups, the surface of the adsorbent is negatively charged, and the adsorbent can perform the actions of adsorption, ion exchange, complexation and the like with heavy metals such as cadmium and the like, so that the bioavailability of the heavy metals is reduced, and the crop absorption is reduced. The precipitant can reduce the bioavailability by regulating the pH of the soil and relieving the acidification of the soil so as to reduce the migration activity of cadmium or fixing the cadmium by coprecipitation. The composite conditioner has the characteristics of small dosage of a single medicament, no secondary pollution, capability of effectively reducing the content of available cadmium in soil on the premise of lower addition amount, good long-term stability and the like.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 95 ℃, adding rice hull biochar, stirring at 95 ℃ for 0.5h, cooling to room temperature, performing suction filtration, drying at 55 ℃ for 24h, grinding, and sieving with a 100-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, rice hull biochar and water is 1:5: 100;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with humic acid and calcium hydroxide according to the mass ratio of 5:12:3 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the effective cadmium in the polluted agricultural land soil is reduced from 1.458mg/L to 1.218 mg/L.
Example 2
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 55 ℃, adding corn biochar, stirring for 3h at 55 ℃, cooling to room temperature, performing suction filtration, drying for 72h at 35 ℃, grinding and sieving with a 100-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, corn biochar and water is 1:2: 40;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with zeolite and calcium carbonate according to the mass ratio of 5:12:3 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the effective cadmium in the polluted agricultural land soil is reduced from 1.458mg/L to 1.23 mg/L.
Example 3
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 45 ℃, adding straw biochar, stirring for 5 hours at 45 ℃, cooling to room temperature, performing suction filtration, drying for 72 hours at 35 ℃, grinding and sieving with a 10-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, straw biochar and water is 1:2: 40;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with bentonite and ferric chloride according to the mass ratio of 5:12:3 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the effective cadmium in the polluted agricultural land soil is reduced from 1.458mg/L to 1.114 mg/L.
Example 4
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 65 ℃, adding rice hull biochar, stirring for 2h at 65 ℃, cooling to room temperature, performing suction filtration, drying for 72h at 35 ℃, grinding and sieving with a 80-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, rice hull biochar and water is 1:2.5: 50;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with sodium humate and ferric sulfate according to the mass ratio of 3:3:4 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the available cadmium in the polluted agricultural land soil is reduced from 1.411mg/L to 0.989 mg/L.
Example 5
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 85 ℃, adding corn biochar, stirring for 1h at 85 ℃, cooling to room temperature, performing suction filtration, drying for 48h at 45 ℃, grinding and sieving with a 80-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, corn biochar and water is 1:5: 50;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with humic acid and iron powder according to the mass ratio of 2:2:1 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the available cadmium in the polluted agricultural land soil is reduced from 1.411mg/L to 1.134 mg/L.
Example 6
(1) Dissolving diethyltriaminepentaacetic acid (DTPA) in water at 55 ℃, adding rice hull biochar, stirring for 3h at 55 ℃, cooling to room temperature, performing suction filtration, drying for 72h at 35 ℃, grinding and sieving with a 100-mesh sieve to obtain DTPA modified biochar; wherein the mass ratio of DTPA, rice hull biochar and water is 1:10: 100;
(2) and (2) uniformly mixing the DTPA modified biochar prepared in the step (1) with sodium humate and calcium oxide according to the mass ratio of 4:5:1 to obtain the cadmium-polluted agricultural land soil composite conditioner.
Adding 2g of the prepared composite conditioner into 100g of naturally air-dried soil of cadmium-polluted farmland around a certain coal mine in Nanchuan Chongqing, adding 100mL of water, uniformly stirring, and standing for 14 days under natural conditions. The content of cadmium in an effective state in the soil is determined according to the standard of determination of elements in an effective state in the soil 8, namely leaching of diethyltriaminepentaacetic acid-inductively coupled plasma emission spectrometry (HJ 804-: after the treatment of the composite conditioner, the content of the available cadmium in the polluted agricultural land soil is reduced from 1.458mg/L to 1.242 mg/L.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (9)
1. The cadmium-polluted agricultural land soil composite conditioner is characterized by comprising the following components in percentage by mass: 25-50% of DTPA modified biochar, 30-60% of adsorbent and 10-40% of precipitator.
2. The composite conditioner for soil polluted by cadmium in agricultural land as claimed in claim 1, wherein said DTPA modified biochar is prepared by the following method: dissolving DTPA in water of 45-95 deg.C, adding biochar, stirring at 45-95 deg.C for 0.5-5h, cooling to room temperature, vacuum filtering, oven drying, grinding, and sieving.
3. The soil composite conditioner for cadmium-polluted agricultural land as claimed in claim 2, wherein the mass ratio of DTPA, biochar and water is 1:2-10: 40-100.
4. The soil composite conditioner for cadmium-polluted agricultural land as claimed in claim 2, wherein the biochar is one of corn biochar, rice hull biochar or straw biochar.
5. The soil composite conditioner for cadmium-polluted agricultural land as claimed in claim 2, wherein the drying is specifically as follows: drying at 35-55 deg.C for 24-72 h.
6. The composite conditioner for soil polluted by cadmium used in agriculture as claimed in claim 2, wherein the size of said sieve is 10-100 mesh.
7. The soil composite conditioner for cadmium-polluted agricultural land as claimed in any one of claims 1 to 6, wherein the adsorbent is one or more of bentonite, zeolite, humic acid or sodium humate.
8. The composite conditioner for soil polluted by cadmium in agricultural land as claimed in any one of claims 1 to 6, wherein said precipitant is one of calcium hydroxide, calcium oxide, calcium carbonate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride or iron powder.
9. The use method of the cadmium-polluted agricultural land soil composite conditioner as claimed in any one of claims 1 to 8, characterized in that the method comprises the following steps: adding 4-20% of the cadmium-polluted agricultural land soil by the amount of the composite conditioner, adding water into the composite conditioner and the cadmium-polluted agricultural land soil, uniformly mixing, and standing for more than 14 days under natural conditions.
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Application publication date: 20210430 |