CN111303900B - Modified charcoal-based soil conditioner for repairing Cd pollution and preparation method and application thereof - Google Patents
Modified charcoal-based soil conditioner for repairing Cd pollution and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified charcoal-based soil conditioner for repairing Cd pollution and a preparation method and application thereof, and belongs to the field of soil treatment. The invention provides a modified biochar-based soil conditioner which is prepared by heating agricultural/industrial wastes and alkaline additives. The soil conditioner after high-temperature reaction can effectively reduce the content of effective Cd in the acidic heavy metal contaminated soil, improve the pH value of the soil, promote the growth of vegetables and reduce the accumulation of heavy metal Cd in the vegetables. Meanwhile, the provided modified biochar-based soil conditioner has the advantages of low cost, convenience and easy obtainment and no secondary pollution.
Description
Technical Field
The invention belongs to the field of soil heavy metal treatment, and particularly relates to a modified charcoal-based soil conditioner for promoting vegetable growth and reducing vegetable Cd accumulation, and a preparation method and application thereof.
Background
With the acceleration of urbanization and industrialization process in China, the influence of human activities on soil environment quality is increasingly intensified, the emission of three wastes in the industries of electroplating, steel, printing and dyeing and the like is increasingly increased, and the heavy metal pollution problem of soil is increasingly highlighted due to unreasonable application of pesticides and fertilizers containing heavy metals in mining and agricultural production. Cadmium (Cd) is the most common heavy metal element in farmland soil pollution at present, and has the characteristics of difficult migration, difficult degradation, easy plant enrichment and the like. The national soil pollution condition survey bulletin issued by the environmental protection department and the national soil resources department indicates that the total exceeding rate of soil pollution in China is 16.1 percent and the exceeding rate of the cultivated land point is 19.4 percent, whereinThe standard exceeding rate of Cd is the highest and is 7%. The heavy metal enrichment condition and the spatial distribution research of the farmland soil in China also show that the contents of Pb, Cd, Cu and Zn in the farmland soil in China have different degrees of enrichment, and the overproof phenomenon generally exists in China, wherein the enrichment of Cd is the most serious. The treatment of heavy metal pollution is a great problem in the world at present, and particularly the remediation of large-area heavy metal polluted farmland soil. The lack of repair materials with wide sources, environmental protection and high efficiency is one of the important reasons for restricting the repair of the heavy metal pollution of the soil at present. In addition, soil acidification is also one of the main problems restricting the sustainable development of agriculture in China, and particularly in the south of the Yangtze river in China, the soil acidification problem is very serious. The area of various acidified soils in China is about 2 hundred million hm2And the area of various acidified soils accounts for about 60 percent in Guangdong province. In recent years, with the development of industry, acid rain precipitation is continuously increased, and soil acidification is further increased due to the abuse of chemical fertilizers, particularly the heavy use of ammonium nitrogen fertilizers, the continuous harvest of crops and the removal of alkaline substances in soil and the like. After the soil is acidified, a large amount of nutrient elements such as Ca, Mg, P and the like in the soil are leached, the activity of heavy metals in the soil is greatly increased, and the heavy metal toxicity in the acid soil is a main factor for inhibiting the growth of crops and reducing the yield of the crops.
Therefore, the development of an acid soil remediation product capable of realizing soil heavy metal passivation is a problem to be solved by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a modified charcoal-based soil conditioner for repairing Cd pollution.
The invention further aims to provide a preparation method of the modified biochar-based soil conditioner.
The invention also aims to provide application of the modified biochar-based soil conditioner.
The invention provides a modified biochar-based soil conditioner for promoting vegetable growth and reducing vegetable Cd accumulation and a preparation method thereof. The existing biochar-based soil conditioner is usually prepared by separately preparing biochar and an alkaline additive and then simply mixing the biochar and the alkaline additive according to different proportions.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, a modified biochar-based soil conditioner is provided, which is prepared by heating agricultural/industrial wastes and alkaline additives under inert gas.
The inventor finds that the method of high-temperature anoxic pyrolysis after mixing the alkaline additive and the biochar raw material according to a certain proportion overcomes the adverse effects of certain toxic and harmful components remained in the alkaline additives such as fly ash, slag powder, steel slag powder, alkaline residue and the like in the industrial production process on soil microorganisms and soil animals and plants. In addition, in the process of temperature rise, the capability of the biological carbon in adjusting soil acidity is enhanced, and the capability of the biological carbon in passivating soil heavy metal is combined, so that the effects of effectively passivating soil heavy metal Cd, reducing the accumulation of heavy metal Cd in vegetables, improving soil acidity and increasing yield and income of vegetables are achieved.
The biochar has the characteristics of porosity, high specific surface area, strong surface adsorption and the like, so that the biochar has a good effect on improving the soil polluted by heavy metals. Conventionally, lime, fly ash, slag powder, steel slag powder, alkaline residue and other alkaline additives are fully mixed with farmland surface soil in modes of ploughing, stirring and the like, so that the pH value of the soil is increased. Therefore, on one hand, the purposes of repairing heavy metal pollution in acid soil and increasing yield and income are achieved by utilizing the outstanding biochemical stability, strong water and fertilizer retention and strong adsorption property of the biochar to heavy metals and simultaneously combining the characteristics of strong basicity of the alkaline additive and supplying Ca, Mg and other nutrient elements required by crops.
According to an embodiment of the present invention, the agricultural/industrial waste is one or more of a biogas byproduct, coconut shells, peanut shells, and rice hulls. In some embodiments, the agricultural/industrial waste material is peanut hulls or rice hulls.
According to the embodiment of the invention, the alkaline additive is one or two of fly ash, slag powder, steel slag powder and alkaline residue.
In some embodiments, the alkaline additive is fly ash and soda industry waste residue.
In a second aspect of the invention, a preparation method of a modified biochar-based soil conditioner is provided, which comprises the following steps:
mixing an alkaline additive with agricultural/industrial waste materials, heating in a nitrogen atmosphere, carrying out heat preservation reaction, and cooling to room temperature to obtain a crude modified biochar-based soil conditioner; grinding and sieving to obtain the modified biochar-based soil conditioner.
According to the embodiment of the invention, the alkaline additives are rinsed, filtered, dried and crushed to have a particle size of less than 5mm before being mixed; the pH value of the dried alkaline additive is 9-12, and the total content of CaO and MgO of the alkaline additive is not less than 50%.
According to the embodiment of the invention, the agricultural/industrial waste is dried and crushed to a particle size of less than 5mm before being mixed.
According to the embodiment of the invention, the mixing ratio of the alkaline additive to the agricultural/industrial waste is 1 (5-50) by mass.
In some embodiments, the mixing ratio of the alkaline additive to the agricultural/industrial waste is 1 (15-30) by mass.
According to the embodiment of the invention, the temperature is raised to 300-600 ℃ in 60 minutes at the speed of 8-12 ℃ per minute under the nitrogen atmosphere.
In some embodiments, the temperature is raised to 450-550 ℃ in 60 minutes at a rate of 8-12 ℃ per minute under a nitrogen atmosphere.
According to the embodiment of the invention, the reaction is carried out for 4-6h after the temperature is raised; in some embodiments, the reaction is carried out for 2-10h after the temperature is raised;
according to the embodiment of the invention, the obtained biochar crude product is ground and then screened by a 40-100 sieve; in some embodiments, the milling is followed by an 80-120 mesh screen.
The third aspect of the invention provides a planting method of a modified biochar-based soil conditioner for promoting vegetable growth and reducing vegetable Cd accumulation.
According to the embodiment of the invention, the application amount of the modified biochar-based soil conditioner is 0.3% -5%; in some embodiments, the modified biochar-based soil conditioner is applied at a rate of 1% to 3%.
In conclusion, compared with the existing heavy metal contaminated soil remediation technology and soil improvement technology, the modified biochar-based soil conditioner disclosed by the invention has the following advantages:
1. has obvious effect of remedying the heavy metal pollution of the soil. The prepared modified biochar-based soil conditioner has the characteristics of loose and porous surface structure, large specific surface area, strong adsorption capacity and the like, and has better passivation effect on soil Cd than that of biochar or alkaline additives used alone.
2. Has obvious effect of improving acid soil. The prepared modified biochar-based soil conditioner is an alkaline material, can obviously improve the pH value of soil, and in addition, the nutrient elements such as calcium, magnesium, silicon and the like in the alkaline additive and the organic carbon in the biochar can obviously improve the soil quality, improve the soil fertility, improve the soil granular structure, promote the growth of crops and achieve the effects of increasing the yield and the income.
3. The agricultural/industrial waste material and the alkaline residue and other raw materials in the invention are selected from industrial and agricultural wastes, and have wide sources, simple process and low cost. All the used raw materials are subjected to harmless treatment, and components which can cause soil pollution and are possibly carried by the raw materials are removed through high-temperature anoxic pyrolysis, so that secondary pollution can not be generated in the application process, the carbon sink of the soil can be increased, and the emission of greenhouse gases is reduced.
The basic physicochemical properties of the modified charcoal-based soil conditioner are as follows: pH value is 10-12, organic carbon content is 34.0-35.13%, quick-acting nitrogen is 99.3-111.6 mg/kg, available phosphorus is 171.26-193.64 mg/kg, quick-acting potassium is 23.0-26.9 g/kg, CaO is more than or equal to 6.5%, and MgO is more than or equal to 1.7%.
Detailed Description
The technical solution of the present invention is clearly and completely illustrated below with reference to the following examples, but is not limited thereto.
Example 1: preparation method of modified charcoal-based soil conditioner
Rinsing the waste residues (also called alkaline residues) in the alkali production industry by using pure water, filtering by using filter paper, drying and crushing to obtain an alkaline residue crude product with the particle size of less than 5 mm; drying and crushing the coconut shell into coconut shell particles with the particle size of less than 5 mm. Respectively weighing 100g of the crude product of the caustic sludge and 1500g of the granular coconut shell, fully mixing the two, putting the mixture into an atmosphere box furnace, vacuumizing the atmosphere box furnace, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and then cooling to room temperature to obtain the crude product of the modified coconut shell biochar-based soil conditioner. Grinding the crude modified coconut shell biochar-based soil conditioner product and sieving the ground product with a 80-mesh sieve to obtain the modified coconut shell biochar-based soil conditioner.
Example 2: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying rice hull, and pulverizing to particle size less than 5 mm. Weighing 100g of the crude alkaline residue product and 1500g of the rice hull granular matter, fully and uniformly mixing, putting into an atmosphere box type furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified rice hull biochar-based soil conditioner. Grinding the crude modified rice hull biochar-based soil conditioner product and sieving the ground product with a 80-mesh sieve to obtain the modified rice hull biochar-based soil conditioner.
Example 3: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; and drying and crushing the biogas byproduct to a particle size of less than 5 mm. Respectively weighing 100g of the crude product of the alkaline residue and 1500g of the granular substance of the biogas byproduct, fully mixing, putting the mixture into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude product of the modified biogas byproduct biochar-based soil conditioner. Grinding the crude product of the modified biogas byproduct biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified biogas byproduct biochar-based soil conditioner.
Example 4: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Weighing 100g of the crude alkaline residue product and 1500g of the peanut shell granules respectively, fully and uniformly mixing, putting into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 5: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Weighing 100g of the crude alkaline residue product and 500g of the peanut shell granules respectively, fully mixing, placing into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 6: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Weighing 100g of the crude alkaline residue product and 1000g of the peanut shell granules respectively, fully mixing, placing into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 7: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Respectively weighing 50g of the crude alkaline residue product and 1250g of the peanut shell granules, fully and uniformly mixing, putting the mixture into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 8: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Respectively weighing 50g of the crude alkaline residue product and 1500g of the peanut shell granules, fully and uniformly mixing, putting into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 9: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Respectively weighing 50g of the crude alkaline residue product and 1750g of the peanut shell granules, fully mixing, placing into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 10: preparation method of modified charcoal-based soil conditioner
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying and crushing until the particle size is less than 5mm to form an alkali residue crude product; drying the peanut shells and crushing the peanut shells to the particle size of less than 5 mm. Respectively weighing 50g of the crude product of the alkaline residue and 2500g of the granular substance of the peanut shell, fully mixing the raw product and the granular substance, putting the raw product and the granular substance into an atmosphere box furnace, vacuumizing the furnace, introducing nitrogen as protective gas, heating the raw product to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling the raw product to room temperature to obtain the crude product of the modified peanut shell biochar-based soil conditioner. Grinding the crude product of the modified peanut shell biochar-based soil conditioner and sieving the ground product with a 80-mesh sieve to obtain the modified peanut shell biochar-based soil conditioner.
Example 11 (comparative example 1): preparation method of biochar
Drying and crushing coconut shells to obtain particles with the particle size of less than 5mm, weighing 1500g, putting the particles into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude coconut shell biochar product. Grinding the crude coconut shell biochar product and sieving the crude coconut shell biochar product with a 80-mesh sieve to obtain a finished coconut shell biochar product.
Example 12 (comparative example 2): preparation method of biochar
Drying and crushing the rice hulls to obtain particles with the particle size of less than 5mm, weighing 1500g of the rice hulls, putting the particles into an atmosphere box type furnace, vacuumizing the atmosphere box type furnace, introducing nitrogen as protective gas, heating the mixture to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling the mixture to room temperature to obtain the crude product of the rice hull biochar. Grinding the obtained coarse rice hull biochar product and sieving the coarse rice hull biochar product with a 80-mesh sieve to obtain a finished rice hull biochar product.
Example 13 (comparative example 3): preparation method of biochar
Drying the biogas byproduct, crushing to obtain particles with a particle size of less than 5mm, weighing 1500g, placing into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at a speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain a biogas byproduct biochar crude product. Grinding the crude product of the biological gas byproduct biochar and sieving the crude product with a 80-mesh sieve to obtain the finished product of the biological gas byproduct biochar.
Example 14 (comparative example 4): preparation method of biochar
Drying peanut shells, crushing until the particle size is less than 5mm, weighing 1500g, placing into an atmosphere box furnace, vacuumizing, introducing nitrogen as protective gas, heating to 450 ℃ within 60 minutes at the speed of 10 ℃ per minute, carrying out heat preservation reaction for 5 hours, and cooling to room temperature to obtain the crude product of the peanut shell biochar. Grinding the crude peanut shell biochar product and sieving the ground peanut shell biochar product with a 80-mesh sieve to obtain a finished peanut shell biochar product.
Example 15 (comparative example 5): preparation method of calcium-magnesium alkaline additive
Rinsing the alkali-making industrial waste residue with pure water, filtering by using filter paper, drying, crushing, grinding and sieving by using a 80-mesh sieve to obtain the calcium-magnesium alkaline additive.
Further experimental verification was made with respect to the above examples.
The detection proves that the basic physicochemical properties of the modified biochar-based soil conditioner are as follows: pH value is 10-12, organic carbon content is 34.0-35.13%, quick-acting nitrogen is 99.3-111.6 mg/kg, available phosphorus is 171.26-193.64 mg/kg, quick-acting potassium is 23.0-26.9 g/kg, CaO is more than or equal to 6.5%, and MgO is more than or equal to 1.7%.
1. Influence of modified charcoal-based soil conditioner on planting of flowering cabbage and planting soil
The soil to be tested in the potting test of this example was typical acidic red soil collected from Shaoguan mines, the pH of the soil was 4.89, and the available Cd content was 2.53 mg/kg. The tested crop is a cabbage heart, and the planting mode is direct seeding.
The treatment is as follows: a control group without any soil conditioner; the soil conditioner prepared in example 1; the soil conditioner prepared in example 2; the soil conditioner prepared in example 3; the soil conditioner prepared in example 4; biochar prepared in example 11; biochar as prepared in example 12; biochar prepared in example 13; biochar as prepared in example 14; biochar prepared in example 15. Each treatment was repeated four times, and was randomly arranged, with the soil conditioner added at 1%.
Before sowing the cabbage heart, the modifier and NPK inorganic fertilizer (N:100mg/kg soil; P)2O5: 80mg/kg soil; k2O: 100mg/kg soil) and target soil, adding tap water (0.32 kg water is added into 1 kg soil), standing and aging the soil for ten days, then sowing the cabbage heart seeds, covering with proper amount of dry soil to wait for seedling emergence, leaving four seedlings per pot of cabbage heart after seedling emergence, and performing subsequent treatments to ensure that the field management and the nutrient management are consistent. After harvesting the flowering cabbage, measuring the biomass of the overground part of each pot of lettuce and the content of Cd, simultaneously collecting the rhizosphere soil of the lettuce, airing, crushing and sieving, and measuring the content of Cd in the soil in an effective state. The measurement results are shown in tables 1 and 2.
TABLE 1 flowering cabbage harvest stage Biomass and Cd content
As shown in table 1, the yield of vegetables can be significantly improved by using the modified charcoal-based soil conditioner under the potting test conditions, wherein the yield improvement effect of the modified charcoal-based soil conditioner prepared in examples 2 and 4 is most obvious, and is 2.67 times and 2.84 times that of the control. Meanwhile, the content of Cd in vegetables can be remarkably reduced by using the modified charcoal-based soil conditioner under the potting test condition, wherein the effect of the modified charcoal-based soil conditioner prepared in example 3 on the reduction of the content of Cd in vegetables is most obvious, and is reduced by 78.9% compared with a control; and secondly, the modified biochar-based soil conditioner prepared in the examples 2, 4 and 13 is reduced by 42.2%, 42.2% and 46.4% compared with the control group. Compared with the simple biochar treatment, the modified biochar-based soil conditioner has stronger effects of increasing the yield of vegetables and reducing the content of Cd in the vegetables. Example 15 treatment with the calcium magnesium alkaline supplement alone also significantly increased the biomass of the vegetables, which was 2.09 times that of the control treatment, but did not significantly reduce the Cd content of the vegetables.
TABLE 2 effective Cd content and pH of the harvested flowering cabbage
As shown in Table 2, the modified charcoal-based soil conditioner can reduce the content of available Cd in soil and increase the pH value of the soil under the condition of pot culture test. The modified biogas byproduct biochar-based soil conditioner prepared in example 3 and the biogas byproduct biochar prepared in example 13 have the most obvious effects, the content of available Cd in soil is respectively reduced by 35.4% and 29.1%, and the pH value is respectively increased by 1.89 and 1.45; the modified biochar-based soil conditioner and the biochar prepared in the examples 1, 2 and 4 have certain effects on reducing the content of Cd in the effective state of soil and improving the pH value when being applied independently. Compared with the treatment of pure biochar and calcium-magnesium alkaline additives, the corresponding modified biochar-based soil conditioner has stronger capabilities of reducing the content of Cd in the soil in an effective state and improving the pH value of the soil.
In summary, the modified charcoal-based soil conditioners prepared in examples 2, 3 and 4 all have obvious effects of reducing the content of Cd in the soil in an effective state and the content of Cd in vegetables, have certain effects of improving the pH value of the soil and the yield of the vegetables, and are suitable for repairing and improving the soil with Cd pollution risk. Example 3 the growth promoting effect of the modified biochar-based soil conditioner prepared in the embodiment is worse than that of the embodiment 2 and the embodiment 4, but the reduction effect of the modified biochar-based soil conditioner on the Cd content in the soil effective state and the Cd content in the vegetable is stronger than that of the embodiment 2 and the embodiment 4, and the raw materials of the embodiment 2 and the embodiment 4 are easier to obtain than the raw materials of the embodiment 3. Therefore, the optimal Cd-contaminated soil conditioner of the present invention is the product prepared in the above examples 2, 3 and 4, and can be selected according to the soil contamination degree and the actual requirement of soil improvement.
2. Influence of modified charcoal-based soil conditioner on crowndaisy chrysanthemum planting and planting soil
The soil tested in the potting test of this example was typical acidic red soil collected from Shaoguan mine area, the soil pH was 4.89, and the available Cd content was 2.53 mg/kg. The tested crop is crowndaisy chrysanthemum, and the planting mode is direct seeding.
The treatment is as follows: a control group without any soil conditioner; the soil conditioner prepared in example 4; the soil conditioner prepared in example 5; the soil conditioner prepared in example 6; the soil conditioner prepared in example 7; the soil conditioner prepared in example 8; the soil conditioner prepared in example 9; the soil conditioner prepared in example 10. Each treatment was repeated four times, and was randomly arranged, with the soil conditioner added at 1%.
Before sowing crowndaisy chrysanthemum, the soil modifier and NPK inorganic fertilizer (N:100mg/kg soil; P) are added2O5: 80mg/kg soil; k2O: 100mg/kg soil) and target soil, adding tap water (0.32 kg water is added into 1 kg soil), standing and aging the soil for ten days, then sowing the seeds of the crowndaisy chrysanthemum, covering with proper amount of dry soil to wait for emergence of seedlings, reserving eight seedlings per pot of the crowndaisy chrysanthemum after emergence of the seedlings, and keeping the field management and the nutrient management of each subsequent treatment consistent. And (4) after the garland chrysanthemum is harvested, measuring the biomass and the Cd content of the overground part of each pot of the garland chrysanthemum. Meanwhile, collecting the rhizosphere soil of the crowndaisy chrysanthemum, airing, crushing and sieving to determine the content of Cd in the effective state of the soil. The measurement results are shown in tables 3 and 4.
TABLE 3 Cowndaisy chrysanthemum harvest period biomass and Cd content
From table 3, the modified biochar-based soil conditioner prepared by mixing different alkaline additives and the agricultural/industrial waste at a dosage ratio has a certain promotion effect on the growth of the crowndaisy chrysanthemum, the dosage ratio of the alkaline additives to the agricultural/industrial waste of 1: 15 to 1: 30 has a remarkable promotion effect on the growth of the crowndaisy chrysanthemum compared with a control group without the modified biochar-based soil conditioner, and the dosage ratio of the alkaline additives to the agricultural/industrial waste of 1: 15 to 1: 50 obviously reduces the accumulation of Cd on the upper part of the crowndaisy chrysanthemum. The effect result of growth of the crowndaisy chrysanthemum and Cd accumulation is integrated, and the modified charcoal-based soil conditioner prepared by high-temperature pyrolysis of the alkaline additive and the agricultural/industrial waste in a mixing ratio of 1: 15-1: 30 is optimal.
TABLE 4 available Cd content and PH value of soil after harvest of Chrysanthemum coronarium
From table 4, it can be seen that the modified biochar-based soil conditioner prepared by mixing different alkaline additives with the dosage ratio of the agricultural/industrial waste has a certain influence on the content of Cd in the effective state and the pH value in the soil, the content of Cd in the effective state of the soil decreases with the increase of the dosage of the agricultural/industrial waste material, and the pH value of the soil increases with the increase of the dosage of the agricultural/industrial waste material. The modified biochar-based soil conditioner prepared by high-temperature pyrolysis of the alkaline additive and the agricultural/industrial waste in a mixing ratio of 1: 15-1: 50 has good results on reduction of effective Cd content in soil and improvement of pH of soil.
By combining the results in tables 3 and 4, when the mixing ratio of the alkaline additive to the agricultural/industrial waste is 1: 15-50, the content of Cd in the soil in the active state is reduced with the increase of the amount of agricultural/industrial waste materials after the modified biochar-based soil conditioner prepared by high-temperature pyrolysis is applied to the soil, and the pH value of the soil is increased with the increase of the amount of agricultural/industrial waste materials, but when the mixing ratio of the agricultural/industrial waste to the alkaline additive exceeds 30: 1, the application of the modified biochar-based soil conditioner has a certain effect of inhibiting the growth of vegetables. Therefore, the modified biochar-based soil conditioner prepared by pyrolysis at the mixing ratio of the alkaline additive to the agricultural/industrial waste of 1: 15-30 is optimal.
3. Influence of modified charcoal-based soil conditioner on lettuce planting and planting soil
The soil tested in the potting test of this example was typical acidic red soil collected from Shaoguan mine area, the soil pH was 4.89, and the available Cd content was 2.53 mg/kg. The test crop is lettuce, and the planting mode is transplanting.
The treatment is as follows: a control group without any soil conditioner; the soil conditioner prepared in example 5, the dosage is 0.3%; the soil conditioner prepared in example 5 is used in an amount of 1%; the soil conditioner prepared in example 5 is used in an amount of 3%; the soil conditioner prepared in example 5 is used in an amount of 5%; the soil conditioner prepared in example 5 was used in an amount of 9%. Four replicates per treatment were randomized.
The soil conditioner and the nitrogen-phosphorus-potassium inorganic fertilizer (N:100mg/kg soil; P2O 5: 80mg/kg soil; K2O: 100mg/kg soil) with each treatment dosage are fully and uniformly mixed with the target soil, tap water (0.32 kg water is added into 1 kg soil) is added, after the soil is placed and aged for ten days, lettuce plantlets are transplanted, 4 plants are planted in each pot, and the field management and the nutrient management of the subsequent treatments are consistent. And (4) after the lettuce is harvested, measuring the biomass of the overground part of each pot of lettuce and the Cd content. Meanwhile, lettuce rhizosphere soil is collected, dried, crushed and sieved, and then the content of Cd in the soil in an effective state is determined. The measurement results are shown in tables 5 and 6.
Table 5: biomass and Cd content of lettuce in harvest period
From table 5, the modified charcoal-based soil conditioner with the dosages of 0.3%, 1%, 3% and 9% has the effect of improving the biomass of the lettuce in the heavy metal contaminated soil, wherein the 1% -3% has the most significant effect of promoting the growth of the lettuce. Meanwhile, the modified charcoal-based soil conditioner with the dosage of 0.3%, 1%, 3% and 9% has a reducing effect on the Cd content in the lettuce overground part in the heavy metal polluted soil, and the reducing effect is improved along with the increase of the dosage of the conditioner.
Table 6: soil available state Cd content and PH value after lettuce harvest
From table 6, the modified charcoal-based soil conditioner with the use amounts of 0.3%, 1%, 3% and 9% has the effect of reducing the content of Cd in the soil in the effective state after harvesting the vegetables, and simultaneously has the effect of improving the acidity of the soil. In the dosage range of the test conditioner, the content of Cd in the effective state of the soil is reduced along with the increase of the dosage of the conditioner, and the pH value of the soil is increased along with the increase of the dosage of the conditioner. By combining the results of the modified charcoal-based soil conditioner on vegetable growth, vegetable Cd accumulation, soil available state Cd and soil pH shown in tables 5 and 6, the reasonable application amount of the modified charcoal-based soil conditioner in the potting test is 1% -3%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A modified biochar-based soil conditioner is characterized in that the modified biochar-based soil conditioner is formed by heating agricultural/industrial wastes and alkaline additives to 600 ℃ under inert gas;
the alkaline additive is one or two of fly ash, slag powder, steel slag powder and alkaline residue;
the agricultural/industrial waste is one or more of biogas byproduct, coconut shell, peanut shell and rice hull.
2. The method for preparing the modified biochar-based soil conditioner as claimed in claim 1, which is characterized by comprising the following steps: mixing an alkaline additive with agricultural/industrial waste materials, heating in a nitrogen atmosphere, carrying out heat preservation reaction, and cooling to room temperature to obtain a crude modified biochar-based soil conditioner; grinding and sieving to obtain the modified biochar-based soil conditioner.
3. The method according to claim 2, wherein the agricultural/industrial waste is dried and pulverized before being mixed.
4. The method of claim 2, wherein the alkaline additive is rinsed, filtered and dried before being mixed; the pH value of the dried alkaline additive is 9-12, so that the total content of CaO and MgO is not lower than 50%.
5. The preparation method of claim 2, wherein the mixing ratio of the alkaline additive to the agricultural/industrial waste is 1 (5-50) by mass.
6. The method as claimed in claim 2, wherein the temperature is raised to 300-600 ℃ in 60 minutes at a rate of 8-12 ℃ per minute under a nitrogen atmosphere.
7. The method as claimed in claim 6, wherein the temperature is raised to 450-550 ℃ in 60 minutes at a rate of 8-12 ℃ per minute under a nitrogen atmosphere.
8. The preparation method according to claim 2, characterized in that the reaction is carried out for 2-10h after the temperature is raised.
9. The preparation method of claim 8, wherein the reaction is carried out for 4-6h after the temperature is raised; the sieve is a sieve with 40-100 meshes.
10. A planting method for reducing the accumulation of Cd in vegetables is characterized by comprising the following steps: uniformly mixing the modified biochar-based soil conditioner as defined in claim 1 with soil, and planting vegetables in the soil after one week; the application amount of the modified charcoal-based soil conditioner is 0.3% -9%.
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