CN105622290B - Biomass charcoal soil heavy metal restoration agent and preparation method and application thereof - Google Patents

Biomass charcoal soil heavy metal restoration agent and preparation method and application thereof Download PDF

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CN105622290B
CN105622290B CN201510989251.1A CN201510989251A CN105622290B CN 105622290 B CN105622290 B CN 105622290B CN 201510989251 A CN201510989251 A CN 201510989251A CN 105622290 B CN105622290 B CN 105622290B
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biomass charcoal
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简秀梅
蒋恩臣
王明峰
许细薇
李治宇
陈晓堃
吴宇健
徐强
宋艳培
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South China Agricultural University
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Abstract

The invention belongs to the technical field of heavy metal contaminated soil conditioners, and particularly relates to a biomass charcoal soil heavy metal restoration agent and a preparation method and application thereof. The preparation method of the biomass charcoal soil heavy metal restoration agent comprises the following steps: (1) respectively drying the chicken manure or the oil tea shell to obtain dried chicken manure or oil tea shell; (2) crushing the chicken manure or the camellia oleifera shell dried in the step (1), heating to 450-550 ℃, then preserving heat for 1h +/-5 min, and cooling to obtain the biomass charcoal soil heavy metal restoration agent. The repairing agent can inhibit the bioavailability of heavy metals in soil, reduce the absorption amount of crops to the heavy metals in the soil, has rich nutrient substances, coordinated and lasting release of nutrient elements and high utilization efficiency of fertilizer nutrients, can effectively improve and fertilize the soil, improves the utilization rate of the fertilizer, increases the content of organic matters in the soil and improves the water and fertilizer retention capacity of the soil.

Description

Biomass charcoal soil heavy metal restoration agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of heavy metal contaminated soil conditioners, and particularly relates to a biomass charcoal soil heavy metal restoration agent and a preparation method and application thereof.
Background
In recent years, biomass carbonization is one of the research hotspots of biomass utilization conversion technology. The biomass carbonization refers to a technology of using biomass charcoal as a target product under the condition of oxygen deficiency and a certain temperature for biomass (such as agricultural and forestry waste, livestock and poultry manure and the like). The biomass charcoal mainly comprises aromatic hydrocarbon and simple substance carbon or carbon with a graphite structure, contains more than 60% of carbon elements, and also comprises H, O, N, S and a small amount of trace elements. The biomass carbon has the advantages of developed pore structure, large specific surface area, more negative charges, high aromaticity, strong adsorption property and high stability.
Based on the characteristics of the biomass charcoal and the thought of ecological cycle agriculture, a plurality of scholars put forward the idea of returning the biomass charcoal to the field, so that the influence of the carbon returning to the field on the soil fertility, the physical and chemical properties and the soil heavy metal adsorption is increasingly concerned, and the method becomes a research hotspot.
A plurality of researches investigate the action effect of returning the biomass charcoal to the field and make a preliminary progress.
Firstly, the biomass charcoal contains a large amount of nutrient elements required by plants, and is suitable for fertility improvement of barren soil. The biomass charcoal has higher C content and higher N, P, K, Ca and Mg content, wherein the nutrient content of the biomass charcoal is higher than that of agriculture and forestry biomass charcoal, and the biomass charcoal can be completely used as a substitute fertilizer.
Secondly, the biomass charcoal can change the physical properties and the structure of the soil, promote the interaction of soil biochemistry and physics chemistry to improve the soil fertility, thereby playing a positive role in promoting the growth of crops. After the biomass charcoal is returned to the field, the volume weight and the hardness of the clay soil can be reduced, so that the soil texture and the farming performance are improved; can also promote the interaction of biochemistry and physics and chemistry to improve the soil fertility and indirectly improve the utilization efficiency of crop nutrients, thereby playing a positive role in promoting the growth of crops. The biomass and organic carbon content of the soil microorganisms returned to the field by the biomass charcoal can be obviously improved; the biomass charcoal is applied to the soil, so that the main root length, the root volume and the fresh weight of the root system of the rice in the early growth stage can be increased, the total absorption area and the active absorption area of the root system of the rice are increased, and the yield-seeking effect is achieved.
In addition, the biomass charcoal has a remarkable adsorption effect on soil heavy metals (such as lead, cadmium, copper and the like), and the effectiveness of the metals is reduced. Researches show that the soil treated by the cotton stalk carbon has obvious adsorption effect on cadmium, and the pH value of the soil is increased along with the increase of the addition amount of the cotton stalk carbon, so that H is increased +In the case of heavy metals in the form of sparingly soluble hydroxides, carbonates or phosphates. Functional groups such as carboxylic acid in the biomass charcoal can promote heavy metals to be fixed in soil.
Livestock and poultry manure and agricultural and forestry wastes are two main biomass charcoal raw materials. At present, the preparation and application research of biomass charcoal taking crop straws as raw materials is more and the research on the preparation and application of the biomass charcoal is less in China. Compared with agriculture and forestry biomass, the livestock and poultry manure is not greatly related to seasons, and the scale of the farm is favorable for centralized utilization of the manure. Keri et al have shown that pyrolysis of animal manure produces biomass char that is alkaline, contains a large number of stable aromatic structures, and is rich in inorganic minerals, and that this biomass char concentrates non-volatile minerals such as P, K, improving soil nutrients and water retention. For example, the energy of the livestock and poultry manure can be efficiently and fully utilized to be converted into high-grade biomass charcoal, and the like, and the method has special significance for realizing sustainable development of animal husbandry and relieving increasingly serious greenhouse effect.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a biomass charcoal soil heavy metal restoration agent.
The invention also aims to provide the biomass charcoal soil heavy metal restoration agent prepared by the preparation method.
The invention further aims to provide application of the biomass charcoal soil heavy metal restoration agent.
The purpose of the invention is realized by the following technical scheme:
A preparation method of a biomass charcoal soil heavy metal restoration agent comprises the following steps:
(1) Respectively drying the chicken manure or the oil tea shell to obtain dried chicken manure or oil tea shell;
(2) Crushing the chicken manure or the camellia oleifera shells dried in the step (1), heating to 450-550 ℃, preserving heat for 1h +/-5 min, and cooling to obtain a biomass charcoal soil heavy metal restoration agent, namely a chicken manure charcoal soil heavy metal restoration agent or a camellia oleifera shell charcoal soil heavy metal restoration agent;
The drying temperature in the step (1) is preferably 40-65 ℃;
The drying time in the step (1) is preferably 20-28 h;
The drying time in the step (1) is further preferably 24 hours;
The water content of the dried chicken manure in the step (1) is 3.84-6.25%;
The water content of the dried oil tea shells in the step (1) is 7.54-8.23%;
The length of the particles of the crushed chicken manure or oil-tea camellia shells in the step (2) is not more than 4 mm;
The heating rate of the heating in the step (2) is 16-18 ℃/min;
The biomass charcoal soil heavy metal restoration agent in the step (2) comprises the following water, volatile matters, ash, fixed carbon, C elements, H elements, N elements, S elements and O elements in percentage by mass:
Figure BDA0000887667880000021
Figure BDA0000887667880000031
The pyrolysis temperature and the heat preservation time in the preparation method are more critical, and have great influence on the final technical effect, such as the structure, industrial analysis and element analysis of the carbon;
The biomass charcoal soil heavy metal restoration agent is applied to the field of soil improvement;
The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement comprises the application of the biomass charcoal soil heavy metal restoration agent in potted soil and the application of the biomass charcoal soil heavy metal restoration agent in field soil;
The application of the biomass charcoal soil heavy metal restoration agent in potting soil comprises the following steps:
Planting in a pot, applying a biomass charcoal soil heavy metal restoration agent in soil according to the charcoal soil proportion of 20-110 g/kg, namely adding 20-110 g of the biomass charcoal soil heavy metal restoration agent per kg of dry soil;
The application of the biomass charcoal soil heavy metal restoration agent in potting soil preferably comprises the following steps:
Sieving all the air-dried potted soil with a 10-mesh sieve, filling 8.6kg of soil (the water content is 12.8 percent, and the weight is 7.5kg of the dry soil) in each pot, mixing the biomass charcoal soil heavy metal restoration agent into the soil according to the charcoal soil proportion of 20-110 g/kg, periodically supplementing water, and planting plants after aging for 14-30 days;
The application of the biomass charcoal soil heavy metal restoration agent in field soil comprises the following steps:
When the thickness of a cultivated soil plough layer (surface layer) is 0.30m, 0.48 t-2.64 t of biomass charcoal soil heavy metal restoration agent is applied to one mu of land;
The application of the biomass charcoal soil heavy metal restoration agent in field soil preferably comprises the following steps:
The cultivated land area per mu is 667m 2The thickness of the crop cultivation layer is 0.30m, and the volume weight of the air-dried soil is 1.2t/m 3Calculating the weight of the air-dried soil needing to be fertilized in one mu of land to be fertilized to be 24t, applying a biomass charcoal soil heavy metal restoration agent with the charcoal soil proportion of 20-110 g/kg to the planting land, and applying 0.48-2.64 t of the biomass charcoal soil heavy metal restoration agent in one mu of land; periodically supplementing water, and after aging for 14-30 days, planting crops;
Compared with the prior art, the invention has the following advantages and effects:
(1) The project selects the chicken manure as one of the biomass charcoal raw materials, the total amount of resources is huge, but the resource utilization technology is relatively deficient. The chicken manure in the Guangdong province breeding industry generates 1000 million tons per year, the resource utilization rate, especially the rapid treatment technology is deficient, the energy utilization rate is only 5% -10%, most of the chicken manure is directly discharged into the environment without being treated, the water eutrophication, the atmosphere pollution and the disease spread are caused, and the soil pollution and the crop toxicity are directly or indirectly caused. The biomass charcoal prepared by pyrolyzing the livestock and poultry manure can improve the economic benefit of the livestock and poultry manure and partially solve the problem of utilization of wastes in the breeding industry.
(2) The biomass charcoal heavy metal soil conditioner provided by the invention can inhibit the bioavailability of heavy metals in soil, reduce the absorption amount of crops to the heavy metals in the soil, has rich nutrient substances, coordinated and lasting release of nutrient elements and high utilization efficiency of fertilizer nutrients, can effectively improve and fertilize the soil, improves the utilization rate of the fertilizer, increases the content of organic matters in the soil, and improves the water and fertilizer retention capacity of the soil.
Drawings
FIG. 1 is an SEM morphology of a chicken manure charcoal soil heavy metal restoration agent and a tea-oil camellia shell charcoal soil heavy metal restoration agent; wherein, CMC: a chicken manure charcoal soil heavy metal restoration agent; COOSC: a tea-oil tree shell carbon soil heavy metal restoration agent.
FIG. 2 is an infrared spectrum of the chicken manure charcoal soil heavy metal restoration agent.
FIG. 3 is an infrared spectrogram of the oil tea shell carbon soil heavy metal restoration agent.
FIG. 4 is an XRD (X-ray diffraction) pattern before and after the reaction of the chicken manure charcoal soil heavy metal restoration agent and copper ions.
FIG. 5 is an XRD (X-ray diffraction) pattern before and after the reaction of the tea-oil camellia shell carbon soil heavy metal restoration agent and copper ions.
Fig. 6 is a result analysis diagram of the effect of CMC with different contents on the heavy metal form of Cu-contaminated soil, wherein EX: an acid exchangeable state (exchangeable); FMO: ferromanganese oxide bound (bound to Fe and Mn oxide); OM: organic bound state (bound to organic matter); RES: residual state (residual).
FIG. 7 is a diagram of analysis results of the effects of different amounts of COOSC on the heavy metal morphology of Cu-contaminated soil; wherein, EX: an acid exchangeable state (exchangeable); FMO: ferromanganese oxide bound (bound to Fe and Mn oxide); OM: organic bound state (bound to organic matter); RES: residual state (residual).
FIG. 8 is an analysis chart of the change of the copper concentration of the pakchoi after the contaminated soil is repaired by the chicken manure charcoal soil heavy metal repairing agent.
FIG. 9 is an analysis diagram of the change of the copper concentration of the pakchoi after the heavy metal restoration agent for the camellia oleifera shell carbon soil restores the polluted soil.
FIG. 10 is a graph showing the analysis of the change in yield of pakchoi planted in the soil contaminated with copper and improved by the chicken manure charcoal soil heavy metal remediation agent.
FIG. 11 is a graph showing the analysis of the change in yield of pakchoi planted in the soil contaminated with copper and improved by the heavy metal remediation agent for tea-oil camellia husk soil.
FIG. 12 is an infrared spectrum analysis diagram of the chicken manure charcoal soil heavy metal restoration agent prepared at different pyrolysis temperatures.
FIG. 13 is an infrared spectrum analysis diagram of the camellia oleifera shell carbon soil heavy metal restoration agent prepared at different pyrolysis temperatures.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Drying the chicken manure or the oil tea shell at 65 ℃ for 24 hours to obtain dried chicken manure or oil tea shell; the water content of the dried chicken manure is 4.05 percent; the water content of the dried oil-tea camellia shells is 7.54%;
(2) Crushing the chicken manure or the tea-oil tree shell with larger block head raw materials dried in the step (1) by using a crusher to ensure that raw material particles participating in pyrolysis reaction are uniform, wherein the length of the crushed particles is not more than 4 mm; then uniformly placing the mixture into a biomass pyrolysis reaction device, heating to 500 ℃, wherein the heating rate is 17 ℃/min; preserving the heat for 1 hour; then cooling to room temperature and taking out to obtain a biomass charcoal soil heavy metal restoration agent, namely a chicken manure charcoal soil heavy metal restoration agent or a tea-oil camellia shell charcoal soil heavy metal restoration agent;
(3) And (3) carrying out industrial analysis, element analysis and nutrient analysis on the biomass charcoal soil heavy metal restoration agent prepared in the step (2), and the results are shown in tables 1 and 2.
Table 1 industrial analysis and elemental analysis of soil heavy metal remediation agent prepared in example 1
Figure BDA0000887667880000051
Table 2 nutrient analysis of soil heavy metal restoration agent prepared in example 1
Figure BDA0000887667880000052
(4) And (3) analyzing the liquid phase adsorption characteristic of the biomass charcoal soil heavy metal restoration agent prepared in the step (2), wherein the methylene blue adsorption value of the chicken manure charcoal soil heavy metal restoration agent is 24.7mg/g, the iodine adsorption value is 457.2mg/g, and the copper ion adsorption value is 63.88 mg/g. The methylene blue adsorption value of the oil tea shell carbon soil heavy metal restoration agent is 24.9mg/g, the iodine adsorption value is 201.6mg/g, and the copper ion adsorption value is 11.05 mg/g.
(5) As shown in fig. 1, the soil heavy metal restoration agent prepared in example 1 has a smooth appearance, a scaly structure, and a small number of open pores on the surface, and causes collapse of part of the pore structure, which may be caused by boiling and bubble formation on the surface before volatile components are removed from the system during pyrolysis.
(6) As shown in Table 3 and figure 2, the chicken manure charcoal soil heavy metal restoration agent is 1420cm -1Near and 875cm -1The absorption peaks are obvious nearby, the former is attributed to antisymmetric stretching vibration of C-O bonds, and the latter is CO 3 2-The two peaks are characteristic peaks of carbonate, indicating that a certain amount of CO is contained 3 2-. 1040cm of chicken manure carbon -1The strong absorption peak is close to the peak and is attributed to the antisymmetric stretching vibration of the P-O bond, which indicates that the phosphate contains a certain amount.
TABLE 3 Infrared spectroscopic analysis of chicken manure charcoal soil heavy metal remediation agent
Figure BDA0000887667880000061
Note: in the table, indicates peaks that can be identified, indicates where the peaks are not evident or are absent.
As shown in Table 4 and FIG. 3, the heavy metal restoration agent for the camellia oleifera shell charcoal soil is 1040cm -1～1007cm-1A certain absorption peak exists nearby, the peak belongs to antisymmetric stretching vibration of a P-O bond, which indicates that the soil heavy metal repairing agent contains a certain amount of phosphate, but the peak strength is inferior to that of the chicken manure charcoal soil heavy metal repairing agent, and the P content of the tea-oil camellia shell charcoal soil heavy metal repairing agent is not as high as that of the chicken manure charcoal soil heavy metal repairing agent.
TABLE 4 Infrared spectroscopic analysis of Camellia oleifera shell carbon soil heavy metal remediation agent
Figure BDA0000887667880000062
Figure BDA0000887667880000071
Note: in the table, indicates peaks that can be identified, indicates where the peaks are not evident or are absent.
(7) Crystal structure of biomass charcoal-XRD
As shown in figure 4, the chicken manure charcoal soil heavy metal restoration agent before the reaction with copper ions has diffraction peaks with larger intensity in the vicinity of 28 degrees 2 theta and 41 degrees 2 theta, and according to the comparison of documents, PDF cards are prepared, and are white phosphorus ores ((Ca, Mg) 3(PO4)2) Characteristic peak. White phosphorus ore ((Ca, Mg) in the vicinity of 2 theta (28 degrees) and 2 theta (41 degrees) of the chicken manure charcoal soil heavy metal restoration agent after the reaction with the copper ions compared with the chicken manure charcoal soil heavy metal restoration agent before the reaction with the copper ions 3(PO4)2) The characteristic peak is diminished or disappeared. The chicken manure carbon soil heavy metal restoration agent has a certain amount of phosphate groups and polyphosphate which are generated by pyrolysis and have negative charges, and participates in the adsorption reaction of carbon on metal ions, so that the complexing ability of the carbon on the metal ions is improved.
As shown in fig. 5, compared with the chicken manure charcoal soil heavy metal restoration agent, the tea-oil tree shell charcoal soil heavy metal restoration agent before the reaction with copper ions is white phosphorus ore ((Ca, Mg) at 2 θ ═ 28 ° and 2 θ ═ 41 ° 3(PO4)2) The intensity of the characteristic peak is obviously weakened. White phosphorus ore ((Ca, Mg)) after reaction with copper ions at 28 ° 2 θ and 41 ° 2 θ 3(PO4)2) The characteristic peaks are also not apparent.
Example 2
(1) Drying the chicken manure or the oil tea shell at 40 ℃ for 28h to obtain dried chicken manure or oil tea shell; the water content of the dried chicken manure is 6.25 percent; the water content of the dried oil-tea camellia shells is 8.05%;
(2) Crushing the chicken manure or the tea-oil tree shell with larger block head raw materials dried in the step (1) by using a crusher to ensure that raw material particles participating in pyrolysis reaction are uniform, wherein the length of the crushed particles is not more than 4 mm; then uniformly placing the mixture into a biomass pyrolysis reaction device, heating to 450 ℃, wherein the heating rate is 16 ℃/min; preserving the heat for 1 hour; then cooling to room temperature and taking out to obtain a biomass charcoal soil heavy metal restoration agent, namely a chicken manure charcoal soil heavy metal restoration agent or a tea-oil camellia shell charcoal soil heavy metal restoration agent;
(3) And (3) carrying out industrial analysis, element analysis and nutrient analysis on the biomass charcoal soil heavy metal restoration agent prepared in the step (2), and the results are shown in tables 5 and 6.
Table 5 industrial analysis and elemental analysis of soil heavy metal remediation agent prepared in example 2
Figure BDA0000887667880000072
Figure BDA0000887667880000081
Table 6 nutrient analysis of soil heavy metal restoration agent prepared in example 2
Figure BDA0000887667880000082
(4) And (3) analyzing the liquid phase adsorption characteristic of the biomass charcoal soil heavy metal restoration agent prepared in the step (2), wherein the methylene blue adsorption value of the chicken manure charcoal soil heavy metal restoration agent is 24.7mg/g, the iodine adsorption value is 308.3mg/g, and the copper ion adsorption value is 47.77 mg/g. The methylene blue adsorption value of the oil tea shell carbon soil heavy metal restoration agent is 22.3mg/g, the iodine adsorption value is 190.6mg/g, and the copper ion adsorption value is 8.87 mg/g.
Example 3
(1) Drying the chicken manure or the oil tea shell at 60 ℃ for 20 hours to obtain dried chicken manure or oil tea shell; the water content of the dried chicken manure is 4.80 percent; the water content of the dried oil-tea camellia shells is 7.85%;
(2) Crushing the chicken manure or the tea-oil tree shell with larger block head raw materials dried in the step (1) by using a crusher to ensure that raw material particles participating in pyrolysis reaction are uniform, wherein the length of the crushed particles is not more than 4 mm; then uniformly placing the mixture into a biomass pyrolysis reaction device, heating to 550 ℃, wherein the heating rate is 18 ℃/min; preserving the heat for 1 hour; then cooling to room temperature and taking out to obtain a biomass charcoal soil heavy metal restoration agent, namely a chicken manure charcoal soil heavy metal restoration agent or a tea-oil camellia shell charcoal soil heavy metal restoration agent;
(3) The biomass charcoal soil heavy metal restoration agent prepared in the step (2) is subjected to industrial analysis, element analysis and nutrient analysis, and the results are shown in tables 7 and 8.
Table 7 industrial analysis and elemental analysis of soil heavy metal remediation agent prepared in example 3
Figure BDA0000887667880000083
Table 8 nutrient analysis of soil heavy metal restoration agent prepared in example 3
Figure BDA0000887667880000091
(4) And (3) analyzing the liquid phase adsorption characteristics of the biomass charcoal soil heavy metal restoration agent prepared in the step (2), wherein the methylene blue adsorption value of the chicken manure charcoal soil heavy metal restoration agent is 24.7mg/g, the iodine adsorption value is 320.34mg/g, and the copper ion adsorption value is 50.72 mg/g. The methylene blue adsorption value of the oil tea shell carbon soil heavy metal restoration agent is 22.6mg/g, the iodine adsorption value is 198.4mg/g, and the copper ion adsorption value is 10.81 mg/g.
Example 4 repair effect of Biomass charcoal soil heavy metal remediation agent on heavy metal contaminated soil
(1) The method has the characteristics that the adsorption of the biomass charcoal soil heavy metal restoration agent to copper in the soil treated by the biomass charcoal soil heavy metal restoration agent is physical and chemical adsorption, the desorption efficiency after heavy metal adsorption is low, and the like.
The biomass charcoal soil heavy metal restoration agent prepared in the embodiment 1 is applied to soil according to different charcoal soil proportions; keeping the field water holding capacity at 65% for 14 days; the experimental design is shown in table 9:
TABLE 9 test design of adsorption of heavy metal in contaminated soil by biomass charcoal soil heavy metal remediation agent
Figure BDA0000887667880000092
Figure BDA0000887667880000101
Note: CMC, a chicken manure charcoal soil heavy metal restoration agent; COOSC, a heavy metal restoration agent for the oil tea shell carbon soil.
(2) Applying biomass charcoal to soil with different addition amounts, and analyzing Cu occurrence morphological change of contaminated soil
In various forms of soil heavy metals, the sequence of the biological effectiveness of the metals is acid extractable state > iron-manganese combined state > organic combined state > residue state;
As shown in fig. 6, after the soil added with the chicken manure charcoal soil heavy metal restoration agent (CMC) with different contents is cultured for 14 days, compared with a control group (CK), the acid extractable state of copper is reduced by 3.35-12.39%; the iron-manganese oxidation bonding state of the copper is reduced by 7.86-41.68 percent; the organic combination state rises by 24.10 to 54.66 percent; except that the CMC-110 increases the copper residue state by 3.17 percent, the CMC with other addition amount reduces the copper residue state content by 1.51 to 10.59 percent.
As shown in fig. 7, the addition of the oil tea hull charcoal soil heavy metal remediation agent (COOSC) with different contents reduced the acid extractable state of the soil Cu by 1.39% -3.78% compared with the control group; the iron-manganese oxidation bonding state of the copper is reduced by 7.08-33.11%; the organic binding state is increased by 15.13 to 29.68 percent; except that COOSC-20 increases the residue state by 5.86%, the other addition amount of COOSC decreases the copper residue state content by 2.64% -6.08%.
Therefore, the chicken manure charcoal soil heavy metal restoration agent or the oil tea shell charcoal soil heavy metal restoration agent is applied to soil, provides a large amount of organic matters for the soil, promotes copper in the soil to form an organic combination state, and reduces the bioavailability of the copper in the soil.
Example 5 influence of Biomass charcoal soil heavy metal remediation agent on Cu absorption value of pakchoi
(1) Applying the biomass charcoal soil heavy metal restoration agent to soil according to different charcoal soil proportions (example 4) for restoration for 14 days, planting pakchoi, and harvesting after 60 days:
(2) Copper concentration change of planted pakchoi after polluted soil is repaired by biomass charcoal soil heavy metal repairing agent
As can be seen from the graph 8, the pakchoi is planted 14 days after the chicken manure charcoal soil heavy metal restoration agent is applied, and from the view point of Cu absorbed by the pakchoi, the Cu absorbed by each kilogram of pakchoi is gradually reduced and the total copper absorbed by each pot of plants is also gradually reduced along with the increase of the application amount of the chicken manure charcoal to each pot of soil of 1 kg. The mass ratio of the chicken manure charcoal soil heavy metal restoration agent to soil is increased from 2% to 14%, the absorption amount of each kilogram of pakchoi is reduced from 41.91mg/kg to 26.40mg/kg, and the total absorption amount of each pot of pakchoi is reduced from 0.17mg/pot to 0.04mg/pot, which shows that under the condition that the copper pollutes the vegetable field soil, the using amount of the chicken manure charcoal soil heavy metal restoration agent for restoration is gradually increased, and the effect of inhibiting the pakchoi from absorbing the copper is more obvious. Mainly reduces the acid extractable state and the iron-manganese oxidation state of copper in the soil and improves the organic binding state of the copper along with the increase of the addition amount of the chicken manure carbon soil heavy metal restoration agent, and the organic binding state is not easy to be biologically absorbed in the soil. Therefore, the chicken manure charcoal soil heavy metal restoration agent can improve the copper-polluted vegetable field soil and inhibit the bioavailability of copper.
As can be seen from fig. 9, after the oil tea hull carbon soil heavy metal restoration agent is applied for 14 days, pakchoi is planted, the Cu concentration of the upper part of the roots of the pakchoi planted for 60 days is not significantly reduced compared with the control, and when the carbon soil ratio is increased from 2% to 14%, the Cu adsorption value of each kilogram of pakchoi is 70.4%, 66.6%, 76.3%, 14.7% and 13.5% higher than that of the control sample without carbon; at the addition of 2 percent and 5 percent, the total Cu adsorption amount of each pakchoi is higher than a contrast value, and at the addition of 8 percent to 14 percent, the total Cu adsorption amount of each pakchoi is lower than the contrast value. The heavy metal restoration agent for the oil tea shell carbon soil can inhibit the pakchoi from absorbing Cu in the soil under the condition of pollution by 8-14%.
(3) Influence of biomass charcoal soil heavy metal restoration agent on yield of pakchoi
As can be seen from FIG. 10, the chicken manure charcoal soil heavy metal restoration agent is applied to the copper-polluted vegetable field soil for restoration, then Chinese cabbages are planted after 14 days, and the Chinese cabbages are harvested after 60 days. Except that the total amount of the harvested pakchoi is increased by 4.21% by adding 2% of CMC (CMC-20), the total amount of the pakchoi is decreased by adding 5% -14% of CMC, and the decrease interval is 20.62% -63.20%.
As can be seen from FIG. 11, the Camellia oleifera shell charcoal soil heavy metal restoration agent is applied to the copper-contaminated vegetable field soil for restoration, and then Chinese cabbages are planted after 14 days and harvested after 60 days. Except that the total amount of the harvested pakchoi is increased by 15.52% by the addition amount of 2% COOSC (COOSC-20), the total amount of the pakchoi is decreased by 5.54% -33.04% by the addition amount of other 5% -14% COOSC.
In conclusion, the proper amount of the biomass charcoal soil heavy metal restoration agent can promote the growth of plants and provide trace elements for the plants, but the excessive addition of the biomass charcoal soil heavy metal restoration agent can inhibit the growth of the plants. From the aspect that the biomass charcoal influences the nutrients of the soil, the comprehensive application of the biomass charcoal soil heavy metal restoration agent as a heavy metal polluted soil restoration agent is further explained, the material source, the input amount and the proportion of the biomass charcoal are adjusted according to the soil nutrients and the crop fertilizer requirement, and the balanced placement of the biomass charcoal soil heavy metal restoration agent and the proper farming management measures is a fundamental way for solving the increase of trace elements in the biomass charcoal soil heavy metal restoration agent in the heavy metal soil restoration.
Comparative examples
(1) Drying the chicken manure or the oil tea shell at 65 ℃ for 24 hours to obtain dried chicken manure or oil tea shell; the water content of the dried chicken manure is 4.05 percent; the water content of the dried oil-tea camellia shells is 7.54%;
(2) Crushing the chicken manure or the tea-oil tree shell with larger block head raw materials dried in the step (1) by using a crusher to ensure that raw material particles participating in pyrolysis reaction are uniform, wherein the length of the crushed particles is not more than 4 mm; then uniformly placing the mixture into a biomass pyrolysis reaction device, heating to 350 ℃ or 650 ℃, and raising the temperature at a rate of 17 ℃/min; preserving the heat for 1 hour; and then cooling to room temperature and taking out to obtain the biomass charcoal soil heavy metal restoration agent, namely the chicken manure charcoal soil heavy metal restoration agent or the camellia oleifera shell charcoal soil heavy metal restoration agent.
As can be seen from FIGS. 12 and 13, the biomass charcoal soil heavy metal restoration agent prepared at the pyrolysis temperature of 500 ℃ in example 1 is 1040cm higher than the biomass charcoal soil heavy metal restoration agent prepared at the pyrolysis temperature of 350 ℃ or 650 ℃ in the comparative example -1And a stronger absorption peak is nearby, which shows that the biomass charcoal contains more phosphate, and the peak is obviously stronger than that of the biomass charcoal pyrolyzed at 350 ℃ or 650 ℃. The oxygen-containing functional groups enable the surface of the biomass charcoal to present hydrophilic, hydrophobic and acid-base buffering capacity, and the properties determine the function of the biomass charcoal in liquid phase adsorption.
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 (6)

1. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that:
The biomass charcoal soil heavy metal restoration agent is prepared by the following method:
(1) Respectively drying the chicken manure or the oil tea shell to obtain dried chicken manure or oil tea shell;
(2) Crushing the chicken manure or the camellia oleifera shells dried in the step (1), heating to 450-550 ℃, preserving heat for 1h +/-5 min, and cooling to obtain a biomass charcoal soil heavy metal restoration agent, namely a chicken manure charcoal soil heavy metal restoration agent or a camellia oleifera shell charcoal soil heavy metal restoration agent;
The water content of the dried chicken manure in the step (1) is 3.84-6.25%; the water content of the dried oil tea shells is 7.54-8.23%;
The biomass charcoal soil heavy metal restoration agent in the step (2) comprises the following water, volatile matters, ash, fixed carbon, C elements, H elements, N elements, S elements and O elements in percentage by mass:
Figure FDA0002088829040000011
2. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that:
The drying temperature in the step (1) is 40-65 ℃; the drying time is 20-28 h.
3. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that:
The heating rate in the step (2) is 16-18 ℃/min.
4. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that: the method comprises the application of the biomass charcoal soil heavy metal restoration agent in potting soil and the application of the biomass charcoal soil heavy metal restoration agent in field soil.
5. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that:
The application of the biomass charcoal soil heavy metal restoration agent in potting soil comprises the following steps:
The method is characterized in that potted planting is adopted, and a biomass charcoal soil heavy metal restoration agent is applied to soil according to the carbon soil proportion of 20-110 g/kg.
6. The application of the biomass charcoal soil heavy metal restoration agent in the field of soil improvement is characterized in that:
The application of the biomass charcoal soil heavy metal restoration agent in field soil comprises the following steps:
When the thickness of the cultivated soil layer is 0.30m, 0.48 t-2.64 t of the biomass charcoal soil heavy metal restoration agent is applied to one mu of land.
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