CN111718723A - Phytic acid modified composite biochar soil conditioner and preparation method and application thereof - Google Patents
Phytic acid modified composite biochar soil conditioner and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a phytic acid modified composite biochar soil conditioner as well as a preparation method and application thereof, wherein the preparation method of the phytic acid modified composite biochar soil conditioner comprises the following steps: 1) mixing agricultural and forestry waste biomass with a phytic acid solution, and preparing phytic acid modified biomass by a coprecipitation method; 2) respectively carrying out pyrolysis, cleaning, drying, crushing and sieving on the phytic acid modified biomass to prepare phytic acid modified biochar; 3) mixing phytic acid modified biochar, lime and chitosan uniformly and sieving to prepare the phytic acid modified composite biochar soil conditioner. The invention fully utilizes the strong adsorption effect of phytic acid and lime on heavy metal cadmium, provides an active point for the adsorption and the holding of the heavy metal cadmium through the large specific surface area and the developed pore structure of the biochar, well bonds the biochar and lime particles through chitosan, and can passivate the cadmium pollution under the acid or alkaline soil condition. The invention can be used for prevention and control treatment of cadmium-polluted farmland soil.
Description
Technical Field
The invention belongs to the technical field of soil conditioners, and particularly relates to a composite biochar soil conditioner modified by phytic acid and a preparation method and application thereof.
Background
Cadmium (Cd) is a heavy metal with high pollution and strong toxicity, has strong mobility in the environment, can be accumulated through a food chain, and has different degrees of harm to animals, plants and people. Rice and corn are main grain crops in China, the problem that Cd in the corn and rice exceeds the standard exists in various areas in China, a large part of Cd ingested by a human body comes from the grain and is difficult to be discharged out of the body along with metabolism of the human body, and if the Cd is continuously accumulated in the human body, the health of the human body is seriously damaged. Therefore, the Cd contamination problem is of great concern.
At present, a great deal of research is carried out on the passivation, adsorption and immobilization of soil heavy metal pollution by using various soil conditioning materials, and the biological effectiveness is reduced. The biochar is widely applied to soil heavy metal pollution regulation due to wide sources, low price and certain adsorption effect. However, the surface activity of the biochar is low, and the adsorption effect of the biochar used alone on the heavy metals in the polluted farmland soil is limited. In addition, compared with a single repairing material, the passivation effect of the heavy metal in the soil can be obviously improved by using a plurality of conditioning materials in a matched mode, and the soil repairing material can be suitable for more soil environments. In addition, the existing soil conditioning materials mostly use high molecular inorganic materials such as polyacrylamide or derivatives thereof as binders, have biotoxicity, and can have certain influence on soil microorganisms, crops and the like after being applied to soil.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a phytic acid modified composite biochar soil conditioner and a preparation method and application thereof.
The invention adopts the following specific technical scheme:
a preparation method of a composite biochar soil conditioner modified by phytic acid comprises the following steps:
1) mixing agricultural and forestry waste biomass with a phytic acid solution, and preparing phytic acid modified biomass by a coprecipitation method;
2) respectively carrying out pyrolysis, cleaning, drying, crushing and sieving on the phytic acid modified biomass to prepare phytic acid modified biochar;
3) and uniformly mixing and sieving the phytic acid modified biochar, lime and chitosan to prepare the phytic acid modified composite biochar soil conditioner.
Preferably, the waste biomass of agriculture and forestry in the step 1) is a mixture of one or more of straw waste biomass, bamboo sawdust and rice husk; before mixing with phytic acid solution, the agricultural and forestry waste biomass is pretreated by cleaning, chopping, sieving by less than 2mm and drying at 60 ℃.
Preferably, the mass fraction of the phytic acid solution in the step 1) is 50-70%, and the chemical molecular formula of the phytic acid is C6H18O24P6The purity is more than or equal to 90 percent; the mass ratio of the agricultural and forestry waste biomass to the phytic acid solution is 1: 1-1: 5.
Preferably, the coprecipitation method in step 1) comprises the following steps: stirring the agricultural and forestry waste biomass and phytic acid solution at the speed of 150rpm for 1-5 hours at normal temperature, then aging at the room temperature for 16-24 hours, and drying at the temperature of 60 ℃ to prepare the phytic acid modified biomass.
Preferably, in the step 2), the pyrolysis temperature is 300-800 ℃, the pyrolysis time is 1-4 hours, the temperature rise rate is 5-20 ℃/min, and the nitrogen introduction rate is 5-30 mL/min.
Preferably, the washing in step 2) is repeated by using deionized water until the pH of the effluent is 5.5-6, so as to completely remove the phytic acid.
Preferably, the lime in the step 3) is one of calcium oxide or calcium hydroxide; the water content of the chitosan is less than 8 percent, the ash content is less than 1 percent, and the viscosity is less than or equal to 300 mpa.s.
Preferably, the mixing manner in the step 3) is as follows: the phytic acid modified biochar and lime are uniformly mixed according to the mass part ratio of 1: 1-5: 1, and then chitosan is added according to the mass part ratio of 100: 1-100: 5 to be uniformly mixed.
The second purpose of the invention is to provide the phytic acid modified composite biochar soil conditioner prepared by any one of the preparation methods, wherein the moisture content of the phytic acid modified composite biochar soil conditioner is less than or equal to 3%, and the content of the phytic acid modified composite biochar soil conditioner passing through a 0.3mm standard sieve is more than or equal to 80%.
The third purpose of the invention is to provide an application of the phytic acid modified composite biochar soil conditioner in treating cadmium-polluted farmland soil.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention uses the agricultural and forestry waste biomass charcoal, has the advantage of recycling waste, and uses the phytic acid to modify the biochar and the lime, thereby greatly improving the holding capacity of the conditioner on the cadmium in the soil and being applied to alkaline or acid farmland soil.
2) The invention adopts nontoxic and biodegradable chitosan as the binder to prepare the cadmium-polluted soil conditioner, which can bind all the components and avoid the problem of secondary pollution to soil.
3) The invention fully utilizes the strong adsorption effect of phytic acid and lime on heavy metal cadmium, provides an active point position for the adsorption and the holding of the heavy metal cadmium through the large specific surface area and the developed pore structure of the biochar, well bonds the biochar and lime particles through chitosan, can passivate the cadmium pollution under the condition of acid or alkaline soil, and can obviously improve the problems of heavy metal pollution of farmlands and the like existing in China at present.
Drawings
FIG. 1 is a flow chart of a preparation process of the phytic acid modified composite biochar soil conditioner.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The preparation method of the phytic acid modified composite biochar soil conditioner is researched by the embodiments 1-3, and specifically comprises the following steps:
example 1
As shown in figure 1, the rice straw is cleaned in advance, cut and sieved to be smaller than 2mm, and dried at 60 ℃ for standby. Adding the rice straws into a phytic acid (70% by mass) solution according to the mass ratio of 1:2 by a coprecipitation method, continuously stirring for 2 hours at the normal temperature of 150rpm, standing for aging for 22 hours at the room temperature, and drying at the temperature of 60 ℃ overnight to obtain the phytic acid modified biomass. Pyrolyzing the phytic acid modified biomass by using a tubular furnace to prepare phytic acid modified biochar, wherein the pyrolysis temperature is 500 ℃; the pyrolysis time is 2 hours; the heating rate is 5 ℃/min, and the nitrogen introducing rate is 25 mL/min. And repeatedly washing the phytic acid modified biochar with deionized water until the pH of an effluent is 5.5-6 so as to completely remove the phytic acid. Oven drying at 60 deg.C for 24 hr, grinding, and sieving to obtain powder with particle size smaller than 0.2 mm. Uniformly mixing the phytic acid modified biochar and lime according to the mass part ratio of 2:1, uniformly mixing the phytic acid modified biochar and the lime with chitosan according to the mass part ratio of 100:1, and sieving to obtain a finished product of the phytic acid modified composite biochar soil conditioner.
Example 2
As shown in figure 1, the rice straw is cleaned in advance, cut and sieved to be smaller than 2mm, and dried at 60 ℃ for standby. Adding the rice straws into a phytic acid (70% by mass) solution according to the mass ratio of 1:1 by a coprecipitation method, continuously stirring for 4 hours at normal temperature of 150rpm, standing for aging for 24 hours at room temperature, and drying at 60 ℃ overnight to obtain the phytic acid modified biomass. Pyrolyzing the phytic acid modified biomass by using a tubular furnace to prepare phytic acid modified biochar, wherein the pyrolysis temperature is 300 ℃; the pyrolysis time is 2 hours; the heating rate is 5 ℃/min, and the nitrogen introducing rate is 25 mL/min. And repeatedly washing the phytic acid modified biochar with deionized water until the pH of an effluent is 5.5-6 so as to completely remove the phytic acid. Oven drying at 60 deg.C for 24 hr, grinding, and sieving to obtain powder with particle size smaller than 0.2 mm. Uniformly mixing the phytic acid modified biochar and lime according to the mass part ratio of 5:1, uniformly mixing the phytic acid modified biochar and the lime with chitosan according to the mass part ratio of 100:5, and sieving to obtain a finished product of the phytic acid modified composite biochar soil conditioner.
Example 3
As shown in figure 1, the rice straw is cleaned in advance, cut and sieved to be smaller than 2mm, and dried at 60 ℃ for standby. Adding the rice straws into a phytic acid (70% by mass) solution according to the mass ratio of 1:5 by a coprecipitation method, continuously stirring for 4 hours at normal temperature of 150rpm, standing for aging for 24 hours at room temperature, and drying at 60 ℃ overnight to obtain the phytic acid modified biomass. Pyrolyzing the phytic acid modified biomass by using a tubular furnace to prepare phytic acid modified biochar, wherein the pyrolysis temperature is 800 ℃; the pyrolysis time is 4 hours; the heating rate is 5 ℃/min, and the nitrogen introducing rate is 25 mL/min. And repeatedly washing the phytic acid modified biochar with deionized water until the pH of an effluent is 5.5-6 so as to completely remove phytic acid impurities. Oven drying at 60 deg.C for 24 hr, grinding, and sieving to obtain powder with particle size smaller than 0.2 mm. Uniformly mixing the phytic acid modified biochar and lime according to the mass part ratio of 1:1, uniformly mixing the phytic acid modified biochar and the lime with chitosan according to the mass part ratio of 100:1, and sieving to obtain a finished product of the phytic acid modified composite biochar soil conditioner.
The passivation effect of the conditioner prepared in the embodiments 1 to 3 on cadmium combined pollution in alkaline paddy soil is researched through the embodiments 4 and 5, and the specific steps are as follows:
example 4
The soil is collected from a certain rice oil tanker in Shimen Zhenlong Liqiao village in Kangxing city of Zhejiang province, and the surface layer of the farmland is 0-20cm, the soil is naturally air-dried and then screened by a 2mm screen, and the basic physicochemical properties of the soil are shown in Table 1. Cdso was applied to the screened soil4The prepared Cd solution enables the content of exogenous Cd to exceed the national soil environmental quality (GB 15618-. Keeping the water capacity of the field to be 80%, culturing for 90d, air-drying, grinding and sieving for 2mm to obtain the soil to be tested.
Fully and uniformly mixing a soil conditioner and test soil to obtain mixed soil, weighing 5kg of mixed soil, and putting the mixed soil into a cylindrical plastic barrel (the diameter is 20cm, the height is 30cm), wherein the specific treatment configuration of the process is as follows: t1:10kg of soil +100g of the conditioner prepared in example 1; t2:10kg of soil +100g of the conditioner prepared in example 2; t3:10kg of soil +100g of the conditioner prepared in example 3; t4, 10kg of soil and 50g of phytic acid modified biochar; t5, 10kg of soil and 50g of common biochar; t6, 10kg of soil and 50g of lime; control (CK) was made without any conditioning agent added. Each treatment was 3 replicates.
Before culturing, a standard sample is set, deionized water is added into soil twice a week, and the application amount is 80% of the field water capacity of the standard sample. And after the culture is finished, determining the content of Cd in the soil in an effective state.
As shown in Table 2, the effective Cd of the paddy soil after the treatment of different conditioners is reduced to different degrees. The conditioner prepared in example 1 reduces Cd in the soil in an effective state to the maximum extent, and the reduction range reaches 60.5%. The 3 conditioners prepared in the embodiments 1-3 can effectively passivate the heavy metal Cd in the soil. The phytic acid modified biochar, the common biochar and the lime can reduce the content of the Cd in the effective state of the soil by independently applying the phytic acid modified biochar, the common biochar and the lime, but the treatment effect is obviously lower than that of the conditioner, the common biochar has the worst treatment effect on the Cd in the effective state of the soil, and the reduction range of the treatment of the materials is respectively 45.9%, 9.3% and 34.9%. Compared with the common conditioner, the phytic acid modified composite biochar soil conditioner prepared by the invention can efficiently passivate Cd pollution of soil.
TABLE 1 basic physicochemical Properties of the soil tested
TABLE 2 Effect of different conditioner treatments on the available cadmium content of the soil
| Treatment of | Cd effective state content (mg/kg) | Reduction ratio (%) |
| CK | 0.189 | / |
| T1 | 0.075 | 60.5 |
| T2 | 0.082 | 56.4 |
| T3 | 0.091 | 51.7 |
| T4 | 0.102 | 45.9 |
| T5 | 0.171 | 9.3 |
| T6 | 0.123 | 34.9 |
Example 5
The soil is collected from a certain rice tanker in Shang Bacun of Juxiang of Longquan, Lishui, Zhejiang province as the surface layer of the farmland, and the soil is 0-20 cm; the soil was naturally air dried and sieved through a 2mm sieve, and the basic physicochemical properties of the soil are shown in table 3. Cdso was applied to the screened soil4The prepared Cd solution enables the content of exogenous Cd to exceed the national soil environmental quality (GB15618-1995) level III standard (1mg/kg), and the content of exogenous Cd in the experiment is 1.5 mg/kg. Keeping the water capacity of the field to be 80%, culturing for 90d, air-drying, grinding and sieving for 2mm to obtain the soil to be tested.
Fully and uniformly mixing a soil conditioner and test soil to obtain mixed soil, weighing 5kg of mixed soil, and putting the mixed soil into a cylindrical plastic barrel (the diameter is 20cm, the height is 30cm), wherein the specific treatment configuration of the process is as follows: t1:10kg of soil +100g of the conditioner prepared in example 1; t2:10kg of soil +100g of the conditioner prepared in example 2; t3:10kg of soil +100g of the conditioner prepared in example 3; t4, 10kg of soil and 50g of phytic acid modified biochar; t5, 10kg of soil and 50g of common biochar; t6, 10kg of soil and 50g of lime; control (CK) was made without any conditioning agent added. Each treatment was 3 replicates.
Before culturing, a standard sample is set, deionized water is added into soil twice a week, and the application amount is 80% of the field water capacity of the standard sample. And after the culture is finished, determining the content of Cd in the soil in an effective state.
As shown in Table 4, the effective Cd of the paddy soil after the treatment of different conditioners is reduced to different degrees. The conditioner prepared in example 1 reduces Cd in the soil in an effective state to the maximum extent, and the reduction range reaches 69.3%. The 3 conditioners prepared in the embodiments 1-3 can effectively passivate the heavy metal Cd in the soil. The phytic acid modified biochar, the common biochar and the lime can reduce the content of the Cd in the effective state of the soil by independently applying the phytic acid modified biochar, the common biochar and the lime, but the treatment effect is obviously lower than that of the conditioner, the common biochar has the worst treatment effect on the Cd in the effective state of the soil, and the reduction range of the treatment of the materials is respectively 51.1%, 38.5% and 57.1%. Compared with the common conditioner, the phytic acid modified composite biochar soil conditioner prepared by the invention can efficiently passivate Cd pollution of soil.
TABLE 3 basic physicochemical Properties of the soil tested
TABLE 4 Effect of different conditioner treatments on soil available cadmium content
| Treatment of | Cd effective state content (mg/kg) | Reduction ratio (%) |
| CK | 0.468 | / |
| T1 | 0.144 | 69.3 |
| T2 | 0.160 | 65.8 |
| T3 | 0.172 | 63.2 |
| T4 | 0.229 | 51.1 |
| T5 | 0.288 | 38.5 |
| T6 | 0.201 | 57.1 |
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 preparation method of a composite biochar soil conditioner modified by phytic acid is characterized by comprising the following steps:
1) mixing agricultural and forestry waste biomass with a phytic acid solution, and preparing phytic acid modified biomass by a coprecipitation method;
2) respectively carrying out pyrolysis, cleaning, drying, crushing and sieving on the phytic acid modified biomass to prepare phytic acid modified biochar;
3) and uniformly mixing and sieving the phytic acid modified biochar, lime and chitosan to prepare the phytic acid modified composite biochar soil conditioner.
2. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein the waste agricultural biomass in the step 1) is a mixture of one or more of straw waste biomass, bamboo dust and rice hulls; before mixing with phytic acid solution, the agricultural and forestry waste biomass is pretreated by cleaning, chopping, sieving by less than 2mm and drying at 60 ℃.
3. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein the mass fraction of the phytic acid solution in the step 1) is 50-70%, and the chemical formula of the phytic acid is C6H18O24P6The purity is more than or equal to 90 percent; the mass ratio of the agricultural and forestry waste biomass to the phytic acid solution is 1: 1-1: 5.
4. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein the operation steps of the coprecipitation method in the step 1) are as follows: stirring the agricultural and forestry waste biomass and phytic acid solution at the speed of 150rpm for 1-5 hours at normal temperature, then aging at the room temperature for 16-24 hours, and drying at the temperature of 60 ℃ to prepare the phytic acid modified biomass.
5. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein the pyrolysis temperature in the step 2) is 300-800 ℃, the pyrolysis time is 1-4 hours, the temperature rise rate is 5-20 ℃/min, and the nitrogen introduction rate is 5-30 mL/min.
6. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein deionized water is used for repeated washing during washing in the step 2) until the pH of an effluent liquid is 5.5-6, so that phytic acid impurities are completely removed.
7. The method for preparing the phytic acid modified composite biochar soil conditioner according to claim 1, wherein lime in the step 3) is one of calcium oxide or calcium hydroxide; the water content of the chitosan is less than 8 percent, the ash content is less than 1 percent, and the viscosity is less than or equal to 300 mpa.s.
8. The preparation method of the phytic acid modified composite biochar soil conditioner according to claim 1, wherein the mixing mode in the step 3) is as follows: the phytic acid modified biochar and lime are uniformly mixed according to the mass part ratio of 1: 1-5: 1, and then chitosan is added according to the mass part ratio of 100: 1-100: 5 to be uniformly mixed.
9. The phytic acid modified composite biochar soil conditioner prepared by the preparation method according to any one of claims 1 to 8 is characterized in that the phytic acid modified composite biochar soil conditioner has the moisture content of less than or equal to 3 percent and the content of more than or equal to 80 percent when the phytic acid modified composite biochar soil conditioner passes through a standard sieve with the thickness of 0.3 mm.
10. The application of the phytic acid modified composite biochar soil conditioner as claimed in claim 9 in treating cadmium-polluted farmland soil.
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