CN109082277B - Cadmium-arsenic composite pollution remediation agent and preparation method and application thereof - Google Patents
Cadmium-arsenic composite pollution remediation agent and preparation method and application thereof Download PDFInfo
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- CN109082277B CN109082277B CN201810936188.9A CN201810936188A CN109082277B CN 109082277 B CN109082277 B CN 109082277B CN 201810936188 A CN201810936188 A CN 201810936188A CN 109082277 B CN109082277 B CN 109082277B
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Abstract
The invention provides a cadmium-arsenic composite pollution repairing agent, which comprises the following components in parts by weight of 10-30: 30-60: 10-40: 1-10 parts of mixed calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3(ii) a Wherein, the humic acid modified clay is prepared by clay acidification, clay alkali metal ionization for acidification and humic acid modification. The invention further provides a preparation method of the cadmium-arsenic composite pollution repairing agent. The method comprises the following steps: (1) activating clay acid; (2) alkali metal ionization of the acidified clay; (3) humic acid modified clay; (4) preparing the cadmium-arsenic composite pollution repairing agent. The cadmium-arsenic composite pollution repairing agent provided by the invention can effectively reduce the activity of cadmium and influence the dissolution of arsenic; the heavy metal adsorption and passivation effect is good, soil organic matters can be increased, the soil structure is improved, and the plant growth is promoted.
Description
Technical Field
The invention belongs to the technical field of agricultural environment conservation and restoration, and particularly relates to a cadmium-arsenic composite pollution restoration agent, and a preparation method and application thereof.
Background
Soil acidification is an expression form of soil degradation, and is an important factor for not only reducing soil fertility but also restricting sustainable development of agricultural production. According to statistics, from the last 80 th century to the present, soil acidification conditions in China are more and more serious, the acidified land area is expanded to be more than 40% of the cultivated land area in China, and flaking often occurs, and particularly in the south of China, the soil acidification phenomenon is more serious due to the fact that the soil is acidic and has much rainwater. The soil acidification can cause the activation of heavy metals such as aluminum, manganese, chromium, cadmium and the like, thereby influencing the growth of plants, such as the phenomena of aluminum poisoning, manganese poisoning and the like, and after the activated heavy metals are absorbed and accumulated by crops, the health of human bodies and animal bodies is harmed through a food chain.
The adjustment of soil acidification is a problem which needs to be solved urgently in the modern agricultural environment protection. The research and study show that: (1) the activity of cadmium in the soil can be effectively reduced by increasing the pH value of the soil, but when the reaction is violent, the pH value is too high, and the pH value of the soil fluctuates greatly, arsenic is dissolved out, and the effectiveness of the arsenic is improved; (2) humic acid is a macromolecular organic substance widely existing in nature, the basic structure of the macromolecular humic acid is an aromatic ring and an alicyclic ring, the ring is connected with functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl and the like, and can selectively adsorb and complex heavy metal ions, but the humic acid is generally insoluble in water and soluble in alkaline solution, so that the passivation effect of the humic acid on heavy metals is limited; (3) the clay material can load organic matters on the surface of clay through organic modification, so that the clay material obtains better heavy metal adsorption effect and adsorption selectivity, but common chitosan and cetyl trimethyl ammonium bromide (CTMAB) and the like have higher price, complex process and less application.
Therefore, it is needed to provide a soil pollution remediation agent with milder reaction, good heavy metal adsorption effect, effectively reduced arsenic availability, and simpler product production process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cadmium-arsenic composite pollution repairing agent and a preparation method and application thereof, and the cadmium-arsenic composite pollution repairing agent provided by the invention can effectively reduce the activity of cadmium and influence the dissolution of arsenic; the heavy metal adsorption and passivation effect is good, soil organic matters can be increased, the soil structure is improved, and the plant growth is promoted.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the cadmium-arsenic composite pollution repairing agent is characterized by comprising the following components in parts by weight of 10-30: 30-60: 10-40: 1-10 parts of mixed calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3(ii) a Wherein, the humic acid modified clay is prepared by clay acid activation, acid activated clay sodium modification and humic acid modification.
Further, the preparation method of the humic acid modified clay specifically comprises the following steps:
s1 Clay acidification
Adding clay material into acid liquor, filtering after acidification, reserving the first time of filtered acid liquor for later use, washing and filtering filter residue with deionized water until no precipitate is generated between the filtrate and NaOH, and drying and crushing the filter residue to obtain acidified clay;
s2 alkali metal ionization of acidified clay
Adding the acidified clay obtained in the step S1 into alkali liquor, filtering after alkali metal ionization treatment, reserving filtered alkali liquor for later use, and drying and crushing filter residues to obtain alkali metal ionized clay;
s3 humic acid modified clay
And (3) adding the alkali metal ionized clay obtained in the step (S2) into a humic acid-containing solution, filtering after humic acid modification treatment, washing the filtered residue with deionized water, adjusting the pH of the filtered residue, drying and crushing to obtain the humic acid modified clay.
Further, the Fe (OH)3The preparation method comprises the following steps: adding hematite powder into the first-time filtering acid liquor obtained in S1, filtering after complete reaction, and taking the filtrate for later use; adjusting the pH of the filtrate to Fe with the filtered alkali solution obtained in S23+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3。
Further, the clay material in S1 is one or more of sepiolite, zeolite, attapulgite, montmorillonite, kaolin, and the like.
Furthermore, the particle size of the clay material is less than or equal to 75 μm.
Further, the mass ratio of the clay material to the acid liquor is 1: 1-20, wherein the concentration of the acid solution is 0.1-10 mol/L.
Further, the acid solution is one or more of sulfuric acid, nitric acid and hydrochloric acid.
Further, the acidification treatment temperature in S1 is 10-40 ℃, and the activation treatment time is 5-120 min.
Further, the ratio of the acidified clay to the lye in S2 is 1: 1-30; the concentration of the alkali liquor is 0.5-10%.
Further, the alkali liquor is NaOH, KOH or Na2CO3、K2CO3One or more of (a).
Further, the alkali metal ionization treatment temperature is 10-40 ℃, and the alkali metal ionization treatment time is 1-30 min.
Further, the ratio of the alkali metal-ionized clay to the humic acid-containing solution in S3 is 1: 1-30; the content of humic acid in the humic acid-containing solution is more than or equal to 1 percent.
Further, the humic acid-containing solution is an aqueous solution prepared from one or more of potassium humate, sodium humate, ammonium humate and nitro humic acid.
Further, the temperature of the humic acid modification treatment is 10-40 ℃, and the treatment time is 5-120 min.
Further, the pH value of the humic acid modified clay is 8-12.
Further, the iron content in the hematite powder is more than or equal to 50 percent; the ratio of the hematite powder to the acid liquor filtered for the first time is 1-20: 100.
further, CaCO in the calcium carbonate3The content is more than or equal to 90 percent; the content of CaO in the silicon-calcium-magnesium fertilizer is more than or equal to 40 percent, the content of effective silicon is more than or equal to 30 percent, and the content of MgO is more than or equal to 5 percent.
Based on the same invention concept, the invention also provides a preparation method of the cadmium-arsenic composite pollution repairing agent, which is characterized by comprising the following steps:
s1 Clay acidification
Adding clay material into acid liquor, filtering after acidification, reserving the first time of filtered acid liquor for later use, washing and filtering filter residue with deionized water until no precipitate is generated between the filtrate and NaOH, and drying and crushing the filter residue to obtain acidified clay;
s2 alkali metal ionization of acidified clay
Adding the acid activated clay obtained in the step S1 into an alkali liquor, filtering after clay alkali metal ionization treatment, reserving filtered alkali liquor for later use, and drying and crushing filter residues to obtain alkali metal ionized clay;
s3 humic acid modified clay
Ionizing the alkali metal obtained in the step S2, adding the alkali metal into a humic acid-containing solution, filtering the solution after humic acid modification, washing the filtered residue with deionized water, adjusting the pH of the filtered residue, drying and crushing the residue to obtain humic acid modified clay;
s4 preparation of cadmium-arsenic composite pollution repairing agent
Calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay obtained from S3, Fe (OH)310-30 parts by weight: 30-60: 10-40: 1-10 to obtain the cadmium-arsenic composite pollution repairing agent.
Further, the Fe (OH)3The preparation method comprises the following steps: adding hematite powder into the first-time filtering acid liquor obtained in S1, filtering after complete reaction, and taking the filtrate for later use; adjusting the pH of the filtrate to Fe with the filtered alkali solution obtained in S23+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3。
Further, in the preparation method, the clay material in S1 is one or more of sepiolite, zeolite, attapulgite, montmorillonite, kaolin, and the like. The particle size of the clay material is less than or equal to 75 mu m. The mass ratio of the clay material to the acid liquor is 1: 1-20, wherein the concentration of the acid solution is 0.1-10 mol/L. The acid liquor is one or more of sulfuric acid, nitric acid and hydrochloric acid. In S1, the acidification treatment temperature is 10-40 ℃, and the activation treatment time is 5-120 min. The ratio of the acidified clay to the lye in S2 is 1: 1-30; the concentration of the alkali liquor is 0.5-10%. The alkali liquor is NaOH, KOH or Na2CO3、K2CO3One or more of (a). The alkali metal ionization treatment temperature is 10-40 ℃, and the alkali metal ionization treatment time is 1-30 min. The ratio of the alkali metal-ionized clay to the humic acid-containing solution in S3 is 1: 1-30; the content of humic acid in the humic acid-containing solution is more than or equal to 1 percent. The humic acid-containing solution is an aqueous solution prepared from one or more of potassium humate, sodium humate, ammonium humate and nitro humic acid. The temperature of the humic acid modification treatment is 10-40 ℃, and the treatment time is 5-120 min. The pH value of the humic acid modified clay is 8-12. What is needed isThe iron content in the hematite powder is more than or equal to 50 percent; the ratio of the hematite powder to the acid liquor filtered for the first time is 1-20: 100. CaCO in the calcium carbonate3The content is more than or equal to 90 percent; the content of CaO in the silicon-calcium-magnesium fertilizer is more than or equal to 40 percent, the content of effective silicon is more than or equal to 30 percent, and the content of MgO is more than or equal to 5 percent.
Based on the same invention concept, the invention also provides an application of the cadmium-arsenic composite pollution repairing agent, and the cadmium-arsenic composite pollution repairing agent is applied to adjustment of acidic soil, particularly adjustment of acidic rice field soil and dry soil. Preferably, the pH of the acidified soil is 4.5-6.0; preferably, the application amount of the cadmium-arsenic composite pollution remediation agent for reconditioning acid soil is 100-200 kg/mu, preferably 150 kg/mu.
According to the research of the invention, the activity of cadmium in soil can be effectively reduced by increasing the pH of the soil, but when the pH is too high, arsenic is dissolved out, and the effectiveness of arsenic is improved, so that the pH of the soil is increased by selecting weak acid salt, the reaction speed is slow, and the influence fluctuation on the pH of the soil is small. In addition, the iron oxide and hydroxide have specific adsorption to arsenic, and can effectively reduce the effectiveness of arsenic. Humic acid is a macromolecular substance which can selectively adsorb and complex heavy metal ions. However, humic acid is generally insoluble in water and soluble in alkaline solution, so that the passivation effect on heavy metals is limited. In addition, the total amount of humic acid is surprisingly large, measured in trillion tons, and is a good source of raw materials for the present invention.
The invention has the beneficial effects that:
the invention provides a cadmium-arsenic composite pollution repairing agent, which has the advantages that: (1) the pH value of the soil is improved, and the dissolution of arsenic is influenced: the calcium carbonate, the calcium silicon fertilizer and the modified humic acid clay are alkaline substances and contain various nutrient elements such as calcium, magnesium, silicon and the like, so that the alkali displacement capacity can be improved, the pH value of the soil is increased, the reaction is mild, the pH value of the soil is not greatly fluctuated, the arsenic dissolution is influenced, and the effectiveness of the arsenic is reduced; (2) passivation of heavy metals, reduction of heavy metal availability: the alkaline substance in the invention can neutralize free acid in soil through alkaline mineral substances, replace hydrogen ions on the aluminosilicate, increase adsorption of soil to cations through supplementing active silicon,the pH value of the soil is increased to promote the coprecipitation of anions and heavy metals, so that the bioavailability of the heavy metals is reduced; the modified humic acid clay can complex and adsorb heavy metals, so that the effectiveness of the modified humic acid clay is reduced; fe (OH)3Can specifically adsorb arsenic and effectively reduce the effectiveness of arsenic; (3) increase soil organic matter, improve soil structure, promote vegetation: the modified humic acid clay can improve the content of organic matters in soil, reduce the volume weight of the soil and improve the structure of the soil; in addition, the invention contains various nutrient elements such as K, Ca, Mg and the like required by plants, and can promote the growth of the plants.
The invention further provides a preparation method of the cadmium-arsenic composite pollution repairing agent, which has the advantages that: (1) the prepared humic acid modified clay has good adsorption performance, is easy to settle and recover, and has simple preparation industry and low cost: firstly, acidizing clay, removing cations among clay crystals, increasing the specific surface area and the pore diameter of micropores of the clay, adsorbing humic acid molecules by using a clay material under an alkaline heat condition, and modifying the surface of the clay to ensure that the humic acid modified clay has selective adsorption performance and higher adsorption capacity on heavy metal ions; the prepared humic acid modified clay adsorbent has good adsorption performance, is easy to settle and recover, is suitable for industrial wastewater treatment and soil remediation, and has simple preparation industry and low cost; (2) the invention prepares Fe (OH)3The method has the advantages that: production of Fe (OH) by using iron ore powder with low waste liquid treatment cost in production process3The purity is increased, the effectiveness is improved, and the effects of waste utilization and cost reduction are achieved; (3) the method comprises the steps of preparing calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3The proportion of the compound formula is obtained by repeated experiments, and the components are matched with each other to play a role in synergy.
The invention further provides an application of the cadmium-arsenic composite pollution repairing agent in adjusting the acidified soil, in particular to adjusting the acidified rice field soil and the drought soil. In the experiment of the application effect of the cadmium-arsenic composite pollution repairing agent on the polluted rice field, the cadmium-arsenic composite pollution repairing agent provided by the invention can effectively improve the pH value of soil and reduce the cadmium and arsenic contents in rice. In addition, the experiment also shows that 100-200kg of the cadmium-arsenic composite pollution repairing agent is preferably added into each mu of acid soil; preferably, 150kg of the cadmium-arsenic composite pollution remediation agent is added to each mu of acid soil.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1 cadmium arsenic composite pollution remediation agent
1) Mixing attapulgite with a raw material according to a mass ratio of 1: adding 10 of the filtrate into 1mol/L sulfuric acid, activating at 25 ℃ for 30min, filtering after activation, reserving the first-time filtered acid solution for later use, washing the obtained filter residue with deionized water for multiple times until the obtained washing solution and NaOH do not generate precipitates (namely, the washing solution is washed till no metal ions exist), drying and crushing to obtain acidified attapulgite;
2) mixing acidified sticky attapulgite in a mass ratio of 1: 10, adding the mixture into a 4% NaOH solution, modifying at 25 ℃ for 30min, filtering after modification, reserving filtered alkali liquor for later use, filtering filter residues, drying and crushing to obtain alkali metal ionized attapulgite;
3) alkali metal ionized attapulgite is prepared by mixing the following components in a mass ratio of 1: 20, adding the mixture into a 5% potassium humate solution, modifying for 60min at 25 ℃, filtering after modification, washing the obtained filter residue with deionized water, adjusting the pH value to 10, drying and crushing to obtain the humic acid modified attapulgite.
4) Mixing hematite powder with a mass ratio of 8: adding 100 parts of the filtrate into the first-time filtered acid solution obtained in the step 1), and filtering the mixture after the reaction is completed to obtain a filtrate for later use;
5) adjusting the pH of the filtrate obtained in the step 4) to Fe by using the filtered alkali liquor obtained in the step 2)3+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3；
6) Calcium carbonate, silicon-calcium-magnesium fertilizer and humic acid modified attapulgiteSoil, Fe (OH)3And (3) adding the following components in percentage by weight of 20: 50: 25: 5, and mixing the components in a weight ratio to obtain the cadmium-arsenic composite pollution repairing agent.
Example 2 cadmium arsenic composite pollution remediation agent
1) Mixing attapulgite with a raw material according to a mass ratio of 1: adding 10 of the filtrate into 1mol/L sulfuric acid, activating at 25 ℃ for 30min, filtering after activation, reserving the first-time filtered acid solution for later use, washing the obtained filter residue with deionized water for multiple times until the obtained washing liquid and NaOH do not generate precipitates (namely, the washing liquid is washed till no metal ions exist), drying and crushing to obtain acidified attapulgite;
2) mixing acidified attapulgite in a mass ratio of 1: 10, adding the mixture into a 4% NaOH solution, modifying at 25 ℃ for 30min, filtering after modification, reserving filtered alkali liquor for later use, filtering, drying and crushing filter residues to obtain the alkali metal ionized attapulgite.
3) Alkali metal ionized attapulgite is prepared by mixing the following components in a mass ratio of 1: 20, adding the mixture into a 5% potassium humate solution, modifying for 60min at 25 ℃, filtering after modification, washing the obtained filter residue with deionized water, adjusting the pH value to 10, drying and crushing to obtain the humic acid modified attapulgite.
4) Mixing hematite powder with a mass ratio of 8: adding 100 parts of the filtrate into the first-time filtered acid solution obtained in the step 1), and filtering the mixture after the reaction is completed to obtain a filtrate for later use;
5) adjusting the pH of the filtrate obtained in the step 4) to Fe by using the filtered alkali liquor obtained in the step 2)3+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3；
6) Calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite and Fe (OH)3And (3) mixing the raw materials in a ratio of 30: 50: 15: 5, and mixing the components in a weight ratio to obtain the cadmium-arsenic composite pollution repairing agent.
Example 3 cadmium arsenic composite pollution remediation agent
1) Mixing attapulgite with a raw material according to a mass ratio of 1: adding 10 of the filtrate into 1mol/L sulfuric acid, activating at 25 ℃ for 30min, filtering after activation, reserving the first-time filtered acid solution for later use, washing the obtained filter residue with deionized water for multiple times until the obtained washing liquid and NaOH do not generate precipitates (namely, the washing liquid is washed till no metal ions exist), drying and crushing to obtain acidified attapulgite;
2) mixing acidified attapulgite in a mass ratio of 1: 10, adding the mixture into a 4% NaOH solution, modifying at 25 ℃ for 30min, filtering after modification, reserving filtered alkali liquor for later use, filtering, drying and crushing filter residues to obtain the alkali metal ionized attapulgite.
3) Alkali metal ionized attapulgite is prepared by mixing the following components in a mass ratio of 1: 20, adding the mixture into a 5% potassium humate solution, modifying for 60min at 25 ℃, filtering after modification, washing the obtained filter residue with deionized water, adjusting the pH value to 10, drying and crushing to obtain the humic acid modified attapulgite.
4) Mixing hematite powder with a mass ratio of 8: adding 100 parts of the filtrate into the first-time filtered acid solution obtained in the step 1), and filtering the mixture after the reaction is completed to obtain a filtrate for later use;
5) adjusting the pH of the filtrate obtained in the step 4) to Fe by using the filtered alkali liquor obtained in the step 2)3+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3；
6) Calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite and Fe (OH)3And (3) in a ratio of 24: 50: 25: 1 to obtain the cadmium-arsenic composite pollution repairing agent.
Example 4 cadmium arsenic composite pollution remediation agent
1) Mixing attapulgite with a raw material according to a mass ratio of 1: adding 10 of the filtrate into 0.1mol/L hydrochloric acid, activating at 25 ℃ for 30min, filtering after activation, reserving the first-time filtered acid solution for later use, washing the obtained filter residue with deionized water for multiple times until no precipitate is generated between the obtained washing solution and NaOH (namely no metal ions are generated), drying and crushing to obtain acidified attapulgite;
2) mixing acidified sticky attapulgite in a mass ratio of 1: 10, adding the mixture into a NaOH solution with the concentration of 1%, modifying for 30min at 25 ℃, filtering after the modification is finished, reserving filtered alkali liquor for later use, filtering filter residues, drying and crushing to obtain alkali metal ionized attapulgite;
3) alkali metal ionized attapulgite is prepared by mixing the following components in a mass ratio of 1: 20, adding the mixture into a potassium humate solution with the concentration of 1%, modifying for 60min at 25 ℃, filtering after modification, washing the obtained filter residue with deionized water, adjusting the pH value to 10, drying and crushing to obtain the humic acid modified attapulgite.
4) Mixing hematite powder with a mass ratio of 8: adding 100 parts of the filtrate into the first-time filtered acid solution obtained in the step 1), and filtering the mixture after the reaction is completed to obtain a filtrate for later use;
5) adjusting the pH of the filtrate obtained in the step 4) to Fe by using the filtered alkali liquor obtained in the step 2)3+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3；
6) Calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite and Fe (OH)3And (3) adding the following components in percentage by weight of 20: 50: 25: 5, and mixing the components in a weight ratio to obtain the cadmium-arsenic composite pollution repairing agent.
Example 5 cadmium arsenic composite pollution remediation agent
1) Mixing attapulgite with a raw material according to a mass ratio of 1: adding 10 of the filtrate into 1mol/L sulfuric acid, activating at 25 ℃ for 30min, filtering after activation, reserving the first-time filtered acid solution for later use, washing the obtained filter residue with deionized water for multiple times until the obtained washing solution and NaOH do not generate precipitates (namely, the washing solution is washed till no metal ions exist), drying and crushing to obtain acidified attapulgite;
2) mixing acidified sticky attapulgite in a mass ratio of 1: 10, adding the mixture into a 4% NaOH solution, modifying at 25 ℃ for 30min, filtering after modification, reserving filtered alkali liquor for later use, filtering filter residues, drying and crushing to obtain alkali metal ionized attapulgite;
3) alkali metal ionized attapulgite is prepared by mixing the following components in a mass ratio of 1: 20, adding the mixture into a 5% potassium humate solution, modifying for 60min at 25 ℃, filtering after modification, washing the obtained filter residue with deionized water, adjusting the pH value to 10, drying and crushing to obtain the humic acid modified attapulgite.
6) Mixing calcium carbonate, a silicon-calcium-magnesium fertilizer, humic acid modified attapulgite and hematite powder in a ratio of 20: 50: 25: 5, and mixing the components in a weight ratio to obtain the cadmium-arsenic composite pollution repairing agent.
Experimental example application effect experiment of cadmium-arsenic composite pollution repairing agent
The cadmium-arsenic composite pollution repairing agent provided in examples 1, 2 and 3 was used for testing.
1. Test site: hunan Pont county Yangqian town of Hunan province.
2. Test time: 6 months in 2017 to 10 months in 2017.
3. And (3) field test design: and selecting field blocks with similar sizes and water systems which do not influence each other for testing. The test is carried out by setting 6 treatments as follows: (1) control treatment 1: the rice field is not polluted, and no treatment measures are taken; (ii) a (2) Control treatment 2: polluting the rice field without treatment measures; (3) test treatment 1: applying 50 kg/mu of cadmium-arsenic composite pollution remediation agent to the polluted rice field 10 days before rice transplanting; (4) test treatment 2: applying 100 kg/mu of cadmium-arsenic composite pollution remediation agent to the polluted rice field 10 days before rice transplanting; (5) test treatment 3: and (3) applying 150 kg/mu of cadmium-arsenic composite pollution remediation agent to the polluted rice field 10 days before rice transplanting. (6) Test treatment 4: and (3) applying 200 kg/mu of cadmium-arsenic composite pollution remediation agent to the polluted rice field 10 days before rice transplanting. The treatments are managed according to the normal cultivation of local rice planting. After harvesting the rice, the rice yield, the soil pH, the arsenic content and the cadmium content of the rice are measured.
4. And (3) test results:
the cadmium-arsenic composite pollution remediation agents provided in examples 1, 2, 3, 4 and 5 were used for testing, and the results are shown in tables 1, 2, 3, 4 and 5, respectively.
Table 1 example 1 improvement effect of cadmium arsenic combined pollution remediation agent on soil and rice
Table 2 example 2 improvement effect of cadmium arsenic combined pollution remediation agent on soil and rice
Table 3 example 3 improvement effect of cadmium arsenic combined pollution remediation agent on soil and rice
Table 4 example 4 improvement effect of cadmium arsenic combined pollution remediation agent on soil and rice
TABLE 5 example 5 improvement effect of cadmium arsenic combined pollution remediation agent on soil and rice
The experimental results shown in tables 1, 2, 3 and 4 show that the cadmium-arsenic composite pollution remediation agent provided by the invention can effectively improve the pH value of soil, improve the yield of rice and simultaneously reduce the cadmium and arsenic content in rice. In addition, the experiment also shows that 100-200kg of the cadmium-arsenic composite pollution repairing agent is preferably added into each mu of acid soil; preferably, 150kg of the cadmium-arsenic composite pollution remediation agent is added to each mu of acid soil. As can be seen from Table 3, the amount of Fe (OH) was reduced3The results show that rice has higher arsenic than other treatments (examples 1, 2 and 4)); from Table 5, Fe (OH)3Has better repairing effect than mineral powder.
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.
Claims (7)
1. The cadmium-arsenic composite pollution repairing agent is characterized by comprising the following components in parts by weight of 10-30: 30-60: 10-40: 1-10 mixed calcium carbonate and calcium silicateMagnesium fertilizer, humic acid modified clay and Fe (OH)3(ii) a Wherein, the humic acid modified clay is prepared by clay acidification, clay alkali metal ionization for acidification and humic acid modification;
the preparation method of the humic acid modified clay specifically comprises the following steps:
s1 Clay acidification
Adding clay material into acid liquor, filtering after acidification, reserving the first time of filtered acid liquor for later use, washing and filtering filter residue with deionized water until no precipitate is generated between the filtrate and NaOH, and drying and crushing the filter residue to obtain acidified clay;
s2 alkali metal ionization of acidified clay
Adding the acidified clay obtained in the step S1 into alkali liquor, filtering after alkali metal ionization treatment, reserving filtered alkali liquor for later use, and drying and crushing filter residues to obtain alkali metal ionized clay;
s3 humic acid modified clay
Adding the alkali metal ionized clay obtained in the step S2 into a humic acid-containing solution, filtering after humic acid modification treatment, washing the filtered residue with deionized water, adjusting the pH of the filtered residue, drying and crushing to obtain humic acid modified clay;
the Fe (OH)3The preparation method comprises the following steps: adding hematite powder into the first-time filtering acid liquor obtained in S1, filtering after complete reaction, and taking the filtrate for later use; adjusting the pH of the filtrate to Fe with the filtered alkali solution obtained in S23+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3。
2. The cadmium-arsenic composite pollution remediation agent of claim 1, wherein: the clay material in S1 is one or more of sepiolite, zeolite, attapulgite, montmorillonite and kaolin;
and/or the particle size of the clay material is less than or equal to 75 mu m;
and/or the mass ratio of the clay material to the acid liquor is 1: 1-20, wherein the concentration of the acid liquor is 0.1-10 mol/L;
and/or the acid solution is one or more of sulfuric acid, nitric acid and hydrochloric acid;
and/or the acidification treatment temperature in S1 is 10-40 ℃, and the activation treatment time is 5-120 min.
3. The cadmium-arsenic composite pollution remediation agent of claim 1, wherein: the ratio of the acidified clay to the lye in S2 is 1: 1-30; the concentration of the alkali liquor is 0.5-10%;
and/or the alkali liquor is NaOH, KOH or Na2CO3、K2CO3One or more of;
and/or the alkali metal ionization treatment temperature is 10-40 ℃, and the alkali metal ionization treatment time is 1-30 min.
4. The cadmium-arsenic composite pollution remediation agent of claim 1, wherein: the ratio of the alkali metal-ionized clay to the humic acid-containing solution in S3 is 1: 1-30; the content of humic acid in the humic acid-containing solution is more than or equal to 1 percent;
and/or the humic acid-containing solution is an aqueous solution prepared from one or more of potassium humate, sodium humate, ammonium humate and nitro humic acid;
and/or the temperature of the humic acid modification treatment is 10-40 ℃, and the treatment time is 5-120 min;
and/or the pH value of the humic acid modified clay is 8-12.
5. The cadmium-arsenic composite pollution remediation agent of claim 1, wherein the iron content of the hematite powder is greater than or equal to 50%; the ratio of the hematite powder to the acid liquor filtered for the first time is 1-20: 100.
6. the preparation method of the cadmium-arsenic composite pollution repairing agent is characterized by comprising the following steps:
s1 Clay acidification
Adding clay material into acid liquor, filtering after acidification, reserving the first time of filtered acid liquor for later use, washing and filtering filter residue with deionized water until no precipitate is generated between the filtrate and NaOH, and drying and crushing the filter residue to obtain acidified clay;
s2 alkali metal ionization of acidified clay
Adding the acidified clay obtained in the step S1 into sodium-containing alkali liquor, filtering after alkali metal ionization treatment, reserving filtered alkali liquor for later use, and drying and crushing filter residues to obtain alkali metal ionized clay;
s3 humic acid modified clay
Adding the alkali metal ionized clay obtained in the step S2 into a humic acid-containing solution, filtering after humic acid modification treatment, washing the filtered residue with deionized water, adjusting the pH of the filtered residue, drying and crushing to obtain humic acid modified clay;
s4 preparation of cadmium-arsenic composite pollution repairing agent
Calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay obtained from S3, Fe (OH)310-30 parts by weight: 30-60: 10-40: 1-10, mixing to obtain a cadmium-arsenic composite pollution repairing agent;
the Fe (OH)3The preparation method comprises the following steps: adding hematite powder into the first-time filtering acid liquor obtained in S1, filtering after complete reaction, and taking the filtrate for later use; adjusting the pH of the filtrate to Fe with the filtered alkali solution obtained in S23+Completely precipitating, filtering, drying and crushing to obtain Fe (OH)3。
7. The application of the cadmium-arsenic composite pollution repairing agent as defined in any one of claims 1 to 5 or the cadmium-arsenic composite pollution repairing agent prepared by the method as defined in claim 6 is characterized in that: the cadmium-arsenic composite pollution remediation agent is used for conditioning acidified soil, including conditioning acidified rice field soil and dry soil; the pH of the acidified soil is 4.5-6.0; the application amount of the cadmium-arsenic composite pollution remediation agent in the process of regulating acid soil is 100-200 kg/mu.
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| CN109909291B (en) * | 2019-04-03 | 2021-03-30 | 中湘环保股份有限公司 | Cadmium-polluted soil remediation device and remediation method |
| CN110016351B (en) * | 2019-05-06 | 2021-03-16 | 湖南泰谷生态工程有限公司 | Preparation method and application of cadmium-arsenic composite pollution repairing agent based on natural macromolecular organic matter |
| CN110194956A (en) * | 2019-05-10 | 2019-09-03 | 湖南泰谷生态工程有限公司 | Organic type cadmium arsenic combined pollution renovation agent and the preparation method and application thereof |
| CN111269722B (en) * | 2020-03-02 | 2021-04-13 | 中南林业科技大学 | Slow-release type repairing agent for treating cadmium-arsenic composite polluted paddy soil and preparation method thereof |
| CN112355041B (en) * | 2020-09-27 | 2022-03-01 | 清华大学 | Preparation method and application of hyperstable mineralizer for treating arsenic pollution |
| CN114014429A (en) * | 2021-09-08 | 2022-02-08 | 铜陵晟泽环保科技有限公司 | Organic-inorganic heavy metal ion trapping agent and preparation method thereof |
| CN114410310A (en) * | 2021-12-29 | 2022-04-29 | 武汉市秀谷科技有限公司 | Foliar blocking agent for reducing cadmium in rice and preparation method thereof |
| CN114774130A (en) * | 2022-04-15 | 2022-07-22 | 哈尔滨工业大学 | Modified clay mineral for repairing arsenic-lead-antimony composite contaminated soil and preparation method and application thereof |
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