CN115744873A - Preparation method and application of in-situ nitrogen-doped magnetically-modified pig manure carbon - Google Patents
Preparation method and application of in-situ nitrogen-doped magnetically-modified pig manure carbon Download PDFInfo
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Abstract
The invention discloses a preparation method and application of in-situ nitrogen-doped magnetically-modified pig manure carbon, and belongs to the technical field of agricultural waste resource utilization and soil improvement. The method specifically comprises the following steps: mixing the dry pig manure powder and the water hyacinth powder, adding an adhesive and deionized water for hydrothermal carbonization, filtering and drying to obtain nitrogen-doped hydrothermal carbon; and then mixing the nitrogen-doped hydrothermal carbon with typha orientalis root powder, and then carrying out high-temperature pyrolysis carbonization to obtain the in-situ nitrogen-doped magnetically-modified pig manure carbon. The invention also provides in-situ nitrogen-doped magnetically modified pig manure carbon prepared by the preparation method and application thereof in soil improvement. The method is economical and efficient, can promote high-value utilization of wastes while being used for soil remediation, does not need to add additional chemical agents in the preparation process, avoids secondary pollution, and belongs to a novel green, environment-friendly and sustainable development process technology.
Description
Technical Field
The invention belongs to the technical field of agricultural waste resource utilization and soil improvement, and particularly relates to a preparation method and application of in-situ nitrogen-doped magnetically-modified pig manure carbon.
Background
The soil is the foundation of agriculture, the soil health refers to the sustainable ability of the soil as an important life system for maintaining the survival of plants, animals and human beings, and along with the increasing population and the rapid development of industry, the random use of untreated domestic garbage, randomly discharged industrial wastewater and agricultural chemical fertilizers threatens the soil health greatly. The biochar is a solid organic substance which is rich in carbon, highly aromatic and high in stability and is produced by pyrolyzing and carbonizing biomass under the condition of complete or partial hypoxia. At present, scholars try to improve the performance of soil restoration by using biological carbon by methods such as adjustment of carbonization conditions, acid-base modification, chemical modification of surface organic functional groups and the like, but the effect is not obvious. In the prior art, a chemical coprecipitation method is commonly used for loading iron ions on the biochar, but the method has high manufacturing cost and complex operation and can cause the problems of metal dissolution and the like.
The water hyacinth serving as an external invasive species has strong growth and reproduction capacity, can extrude living space of animals and plants in a water body, causes great harm to the survival and growth, and can cause social problems such as blockage of farmland irrigation, congestion of river channels and the like. In addition, the cattail is a perennial aquatic or marsh herbaceous plant, grows rapidly, and is a species of the wetland superiority in China. The cattail has developed root system, higher iron content and stronger tolerance capability to a plurality of metals such as Cd, cr and the like, so the cattail is widely used in the artificial wetland as a phytoremediation technology. However, at present, there is a few combination of the above two plants into the improvement of charcoal performance.
Therefore, how to combine and utilize the biochar, the water hyacinth and the cattail root to achieve the performance of soil remediation is a technical problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of in-situ nitrogen-doped magnetically-modified pig manure carbon.
In order to realize the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon, which comprises the following steps:
(1) Mixing the dry pig manure powder and the water hyacinth powder, adding an adhesive and deionized water for hydrothermal carbonization, filtering and drying to obtain nitrogen-doped hydrothermal carbon;
(2) And mixing the nitrogen-doped hydrothermal carbon with typha orientalis root powder, and then carrying out high-temperature pyrolysis carbonization to obtain the in-situ nitrogen-doped magnetically-modified pig manure carbon.
Has the advantages that: the in-situ nitrogen-doped magnetically-modified pig manure carbon provided by the invention has a loose and porous structure and higher surface adsorption performance, and meanwhile, the surface functional groups are rich, so that the carbon has good agricultural effects of loosening soil, improving soil structure and retaining water and fertilizer, and the quality of low-fertility soil can be obviously improved; the invention takes the livestock and poultry manure, the pig manure, the waste biomass water hyacinth and the cattail root as raw materials, wherein the water hyacinth has stronger specificity to the absorption of the nutrition of nitrogen and phosphorus elements, and the water hyacinth is used as a nitrogen source to be doped into the biochar, thereby not only effectively solving the damage of the water hyacinth, but also improving the nitrogen content of the biochar, modifying the surface polarity of the biochar, improving the adsorption capacity of the biochar to ionic charges and effectively reducing the surface electronegativity of the biochar. The cattail root has high iron content and strong metal tolerance to various metals, so that the resource utilization of the waste biomass can be realized, the waste pollution control can be realized, and the economic cost is low.
Further, the dry pig manure powder in the step (1) is: dehydrating, pickling, drying and crushing pig manure to obtain dry pig manure powder; the water hyacinth powder is as follows: cleaning, crushing and drying the water hyacinth to obtain water hyacinth powder; the cattail root powder is as follows: cleaning, crushing and drying the cattail root to obtain cattail root powder.
Has the advantages that: the raw materials adopted by the invention are all based on agricultural and forestry wastes, and the high-value utilization of resources is realized. The method comprises the steps of dehydrating, pickling, drying and crushing the raw material pig manure, and aims to purify the raw material pig manure so as to remove impurities; wherein the acid wash is to wash out the labile metal ions which are easily dissolved.
Further, the dehydration is: dehydrating the pig manure until the water content is 80-85%; the pickling solution adopted by pickling is H 3 PO 4 Solution or HNO 3 The concentration of the pickling solution is 1-3mol/L; the drying temperature of the pig manure is 85-100 ℃, and the drying time is 12-20h; the crushing is as follows: pulverizing to particle size less than 0.1mm; the drying temperature of the water hyacinth and the cattail root is 90-105 ℃, and the water hyacinth and the cattail root are dried until the water content is 0%; the powder is crushed and sieved by a 100-mesh sieve.
Further, the mass ratio of the dry pig manure powder to the water hyacinth powder in the step (1) is 1: (2.5-4); the adhesive is NaSO 4 And the addition amount is 0.5 to 1.5 percent of the sum of the dry pig manure powder and the water hyacinth powder; the addition amount of the deionized water is 60-90mL.
Further, the hydrothermal carbonization in the step (1) is: reacting for 18-24h under the conditions that the heating rate is less than or equal to 5 ℃/min and the temperature is 180-250 ℃; the drying temperature is 85-100 ℃, and the drying time is 24h.
Furthermore, the water content of the hydrothermal charcoal after filtering in the step (2) is 10-25%, and the nitrogen doping amount in the prepared nitrogen-doped hydrothermal charcoal is 3-5% after drying.
Further, the mass ratio of the nitrogen-doped hydrothermal carbon to the cattail root powder in the step (2) is 4: (1-2); before the high-temperature pyrolysis, 100-200mL of 1-3mol/L hydrochloric acid solution is firstly put into the high-temperature pyrolysis reactor to be uniformly dispersed, and then the high-temperature pyrolysis reactor is dried for 60-120min at the temperature of 85-100 ℃ and is added with N 2 Is high-temperature pyrolysis carbonization in a protective gas environment.
Further, the high temperature pyrolysis is carbonized to: heating to 400-600 deg.C at a heating rate of 10-15 deg.C/min, and sealing for 2-5h; the iron loading amount of the in-situ nitrogen-doped magnetically-modified pig manure carbon is 1-2%.
Further, after the pyrolysis and carbonization at the high temperature in the step (2), the obtained substance is added into 100-200mL of NaOH solution with the concentration of 1-3mol/L, the solution is kept at the temperature of 80 ℃ for 2-4h, the residual NaOH solution is washed by deionized water, and then the solution is dried at the temperature of 85-100 ℃ for 24h.
The invention also provides the in-situ nitrogen-doped magnetically-modified pig manure carbon prepared by the preparation method of any one of the in-situ nitrogen-doped magnetically-modified pig manure carbons.
The invention also provides application of the in-situ nitrogen-doped magnetically-modified pig manure carbon in soil improvement.
Compared with the prior art, the invention has the following beneficial effects:
the in-situ nitrogen-doped magnetically-modified pig manure carbon is prepared from livestock and poultry manure, waste biomass water hyacinth and typha root as raw materials by hydrothermal carbonization, magnetic modification and other technologies. The magnetically modified biochar has larger specific surface area and more abundant oxygen-containing functional groups, wherein the specific surface area can reach 75m 2 The electron transfer efficiency in the microbial degradation process of the soil rhizosphere can be improved. The biochar after magnetic modification can be controlled by an external magnetic field, so that the biochar is easy to separate and secondary pollution is reduced. Furthermore, the invention adopts hydrothermal carbonizationAnd high-temperature carbonization and other technologies, the in-situ nitrogen-doped magnetically modified pig manure carbon is prepared, is applied to soil improvement, is economical and efficient, is easy to operate in the preparation process, and is suitable for soil improvement engineering application or existing engineering improvement.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is electron microscope images of in-situ nitrogen-doped magnetically modified pig manure carbon prepared in example 1 and comparative example 2, wherein a is an electron microscope image of in-situ nitrogen-doped magnetically modified pig manure carbon prepared in example 1, and b is an electron microscope image of in-situ nitrogen-doped magnetically modified pig manure carbon prepared in comparative example 2;
fig. 2 is an XRD spectrum of the in-situ nitrogen-doped magnetically modified pig manure carbon prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
A preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon comprises the following steps:
1) Raw material treatment: dehydrating raw material pig manure until the water content is 80-85%, and then adopting 1-3mol/L H 3 PO 4 Or HNO 3 Pickling the solution, stirring slowly for 3-5h by a stirrer, stirring quickly for 1-2h, drying in an oven at 85-100 ℃ for 12-20h, and crushing to obtain dry pig manure powder with the grain size of less than 0.1 mm. Cleaning water hyacinth and cattail root with deionized water, pulverizing into powder, sieving with 100 mesh sieve, drying in an oven at 90-105 deg.C until the water content is 0%, to obtain water hyacinth powder and cattail root powder.
2) Hydrothermal carbonization: mixing the dry pig manure powder and the water hyacinth powder according to a mass ratio of 1: (2.5-4) mixing, adding NaSO 4 As the adhesive, the mass of the adhesive is 0.5-1.5% of the sum of the mass of the dry pig manure powder and the mass of the water hyacinth powder. Adding 60-90mL of deionized water, mixing, placing into a sealed high-pressure hydrothermal reaction kettle, performing hydrothermal carbonization at a heating rate of not more than 5 ℃/min, at a hydrothermal reaction temperature of 180-250 ℃ for 18-24h, filtering by a vacuum pump to obtain hydrothermal biochar with a water content of 10-25%, and drying at 85-100 ℃ for 24h to obtain nitrogen-doped hydrothermal carbon with a nitrogen doping amount of 3-5%.
3) Magnetic modification: mixing the nitrogen-doped hydrothermal carbon and the cattail root powder according to a mass ratio of 4: (1-2), uniformly mixing, uniformly dispersing by adopting 100-200mL hydrochloric acid solution with the concentration of 1-3mol/L, drying at 85-100 ℃ for 60-120min, carrying out high-temperature pyrolysis carbonization, heating at the rate of 10-15 ℃/min, keeping the temperature of 400-600 ℃ in a closed carbonization process for 2-5h, adding the carbonized product into 100-200mL NaOH solution with the concentration of 1-3mol/L, keeping the temperature at 80 ℃ for 2-4h, washing with deionized water, and drying at 85-100 ℃ for 24h to obtain the in-situ nitrogen-doped magnetically modified pig manure carbon with the iron loading amount of 1-2%.
The reagents used in the following examples of the invention are all commercially available. The sources of the pig manure, the water hyacinth and the cattail root are not limited.
Example 1
A preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon comprises the following steps:
(1) Pretreatment of raw materials: dehydrating pig manure until the water content is 80%, and then adopting 1mol/L HNO 3 Pickling the solution, drying at 100 ℃ for 20h, and crushing to obtain dry pig manure powder with the grain size of less than 0.1mm;
cleaning water hyacinth with deionized water, then crushing into powder, sieving with a 100-mesh sieve, putting into a drying oven at 100 ℃, and drying until the water content is 0% to obtain water hyacinth powder;
cleaning cattail root with deionized water, then crushing into powder, sieving with a 100-mesh sieve, putting into a drying oven at 100 ℃, and drying until the water content is 0% to obtain cattail root powder.
(2) Mixing the dry pig manure powder and the water hyacinth powder according to the mass ratio of 1 4 Wherein the binder is NaSO 4 Adding 60mL of deionized water, mixing, putting the mixture into a closed high-pressure hydrothermal reaction kettle with the heating rate of less than or equal to 5 ℃/min and the temperature of 200 ℃ for hydrothermal carbonization reaction for 20 hours, filtering by using a vacuum pump to obtain hydrothermal biochar with the water content of 20%, drying at the temperature of 85 ℃ for 24 hours to obtain the nitrogen-doped hydrothermal carbon。
(3) Mixing the nitrogen-doped hydrothermal carbon and the cattail root powder according to a mass ratio of 4 2 Carrying out high-temperature pyrolysis carbonization in a protective gas environment, wherein the conditions of the high-temperature pyrolysis carbonization are as follows: heating to 400 ℃ at the heating rate of 12 ℃/min, sealing and keeping for 2h, finally adding the substance subjected to high-temperature pyrolysis and carbonization into 150mL of NaOH solution with the concentration of 1mol/L, stirring for 2h at 80 ℃, washing the residual NaOH solution with deionized water, and drying for 24h at 100 ℃ to obtain the in-situ nitrogen-doped magnetically modified pig manure carbon. Wherein, the electron micrograph of the prepared in-situ nitrogen-doped magnetically-modified pig manure carbon is shown as a part a in figure 1, and the XRD map is shown as figure 2.
As can be seen from figure 2, the XRD patterns of the in-situ nitrogen-doped magnetically-modified pig manure carbon all show 5 typical Fe 3 O 4 Absorption peaks (220), (311), (400), (511) and (440), respectively, corresponding to 2 θ of 30.4, 35.46, 43.14, 57.40 and 62.53, corresponding to Fe 3 O 4 The standard XRD spectrum of the magnetic iron oxide proves that the iron oxide is mainly magnetic Fe 3 O 4 The content was 1.3%, and the nitrogen content was 3.6%.
Example 2
A preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon comprises the following steps:
(1) Pretreatment of raw materials: dehydrating pig manure until the water content is 83%, and then adopting 2mol/L H 3 PO 4 Pickling the solution, drying at 95 ℃ for 12h, and crushing to obtain dry pig manure powder with the particle size of less than 0.1mm;
cleaning water hyacinth with deionized water, then crushing into powder, sieving with a 100-mesh sieve, putting into a drying oven at the temperature of 90 ℃, and drying until the water content is 0% to obtain water hyacinth powder;
cleaning typha root with deionized water, then crushing to powder, sieving with a 100-mesh sieve, putting into a drying oven at 90 ℃, and drying until the water content is 0%; to obtain the cattail root powder.
(2) Mixing the dry pig manure powder and the water hyacinth powder according to the mass ratio of 1 4 Wherein the binder is NaSO 4 The mass of the nitrogen-doped hydrothermal carbon is 0.5 percent of the sum of the mass of the dry pig manure powder and the mass of the water hyacinth powder, 80mL of deionized water is added for mixing, then the mixture is put into a sealed high-pressure hydrothermal reaction kettle with the heating rate of less than or equal to 5 ℃/min and the temperature of 180 ℃ for hydrothermal carbonization reaction for 24 hours, then a vacuum pump is adopted for filtering to obtain hydrothermal biochar with the water content of 25 percent, and the hydrothermal biochar is dried for 24 hours at the temperature of 90 ℃ to obtain the nitrogen-doped hydrothermal carbon.
(3) Mixing the nitrogen-doped hydrothermal carbon and the cattail root powder according to the mass ratio of 4 to 2 to obtain a mixture, firstly putting the mixture into 100mL hydrochloric acid solution with the concentration of 2mol/L to uniformly disperse the mixture, then drying the mixture at the temperature of 85 ℃ for 120min, and then adding N into the mixture 2 The high-temperature pyrolysis carbonization is carried out in the environment of protective gas, wherein the conditions of the high-temperature pyrolysis carbonization are as follows: heating to 500 ℃ at the heating rate of 10 ℃/min, sealing and keeping for 4h, finally adding the substance subjected to high-temperature pyrolysis and carbonization into 100mL of 2mol/L NaOH solution, stirring at 80 ℃ for 3h, washing the residual NaOH solution with deionized water, and drying at 90 ℃ for 24h to obtain the in-situ nitrogen-doped magnetically modified pig manure carbon.
Example 3
A preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon comprises the following steps:
(1) Pretreatment of raw materials: dehydrating pig manure until the water content is 85 percent, and then adopting 3mol/L HNO 3 Pickling the solution, drying at 85 ℃ for 16h, and crushing to obtain dried pig manure powder with the grain size of less than 0.1mm;
cleaning water hyacinth with deionized water, then crushing into powder, sieving with a 100-mesh sieve, putting into a drying oven with the temperature of 105 ℃, and drying until the water content is 0% to obtain water hyacinth powder;
cleaning cattail root with deionized water, then crushing into powder, sieving with a 100-mesh sieve, placing into a drying oven at 105 ℃, and drying until the water content is 0% to obtain cattail root powder.
(2) Drying the aboveMixing the pig manure powder and the water hyacinth powder according to the mass ratio of 1 4 Wherein the binder is NaSO 4 The mass of the nitrogen-doped hydrothermal carbon is 1.5% of the sum of the mass of the dry pig manure powder and the mass of the water hyacinth powder, then 90mL of deionized water is added for mixing, then the mixture is placed into a closed high-pressure hydrothermal reaction kettle with the heating rate of less than or equal to 5 ℃/min and the temperature of 250 ℃ for hydrothermal carbonization reaction for 24 hours, then a vacuum pump is adopted for filtering to obtain hydrothermal biochar with the water content of 10%, and the hydrothermal biochar is dried for 24 hours at the temperature of 100 ℃ to obtain the nitrogen-doped hydrothermal carbon.
(3) Mixing the nitrogen-doped hydrothermal carbon and the cattail root powder according to the mass ratio of 4 to 1 to obtain a mixture, firstly putting the mixture into 200mL hydrochloric acid solution with the concentration of 3mol/L to uniformly disperse the mixture, then drying the mixture at the temperature of 100 ℃ for 60min, and then adding N into the mixture 2 The high-temperature pyrolysis carbonization is carried out in the environment of protective gas, wherein the conditions of the high-temperature pyrolysis carbonization are as follows: heating to 600 ℃ at the heating rate of 15 ℃/min, sealing and keeping for 5h, finally adding the substance subjected to high-temperature pyrolysis and carbonization into 200mL of NaOH solution with the concentration of 3mol/L, stirring for 4h at 80 ℃, washing the residual NaOH solution with deionized water, and drying for 24h at 85 ℃ to obtain the in-situ nitrogen-doped magnetically modified pig manure carbon.
Comparative example 1
The preparation method of the in-situ nitrogen-doped magnetically-modified pig manure carbon is only different from that of the embodiment 1 in that:
(3) Mixing the nitrogen-doped hydrothermal carbon and the cattail root powder according to the mass ratio of 4 to 1 to obtain a mixture, firstly putting the mixture into 150mL hydrochloric acid solution with the concentration of 1mol/L to uniformly disperse the mixture, then drying the mixture at the temperature of 90 ℃ for 100min, and then adding N into the mixture 2 The high-temperature pyrolysis carbonization is carried out in the environment of protective gas, wherein the conditions of the high-temperature pyrolysis carbonization are as follows: heating to 400 ℃ at the heating rate of 12 ℃/min, and sealing and keeping for 2 hours to obtain the in-situ nitrogen-doped magnetically modified pig manure carbon.
The rest of the procedure was the same as in example 1.
Comparative example 2
A preparation method of common pig manure charcoal comprises the following steps:
dehydrating pig manure to water content of 85%, and then adopting 3mol/L HNO 3 Pickling the solution, drying at 85 deg.C for 16 hr, and pulverizing to particle size less than 0.1mm to obtain dried pig manure powder. Mixing 5g of dry pig manure powder with 60mL of deionized water, putting the mixture into a closed high-pressure hydrothermal reaction kettle with the heating rate of less than or equal to 5 ℃/min and the temperature of 250 ℃ for hydrothermal carbonization reaction for 24 hours, filtering the mixture by using a vacuum pump to obtain hydrothermal biochar with the water content of 10%, and drying the hydrothermal biochar at the temperature of 100 ℃ for 24 hours to obtain the pig manure hydrothermal carbon. In the presence of N 2 Carrying out high-temperature pyrolysis carbonization in a protective gas environment, wherein the conditions of the high-temperature pyrolysis carbonization are as follows: raising the temperature to 600 ℃ at the heating rate of 15 ℃/min, and sealing and keeping the temperature for 5 hours to finally obtain the pig manure carbon.
The electron micrograph of the prepared common pig manure carbon is shown as part b in figure 1.
As can be seen from the analysis of figure 1, compared with the common pig manure carbon, the in-situ nitrogen-doped magnetically-modified pig manure carbon prepared by the method has a porous structure, and the specific surface area can reach 75m 2 The metal oxide is embedded in the pores, so that more adsorption sites and higher metal binding capacity can be provided for reaction, and the electron transfer efficiency in the microbial degradation process of the soil rhizosphere is promoted.
Effect verification:
the influence of the in-situ nitrogen-doped magnetically modified pig manure carbon prepared in examples 1 to 3 and the pig manure carbon prepared in comparative examples 1 to 2 on soil and crops when applied was analyzed by a field test analysis method. The optimal application amount of the prepared in-situ nitrogen-doped magnetically-modified pig manure carbon is determined according to the physicochemical properties of the soil, the application proportion is 2%, and the test results are shown in table 1.
TABLE 1 efficacy of in-situ nitrogen-doped magnetically modified pig manure charcoal for soil improvement and yield increase
The data in table 1 show that by applying the in-situ nitrogen-doped magnetically modified pig manure carbon prepared in the embodiment 1 of the invention, the physical and chemical properties of soil are improved, the volume weight of the soil is reduced by 18.1%, while the volume weight of the common pig manure carbon is reduced by only 4.7%, and the soil improved by the in-situ nitrogen-doped magnetically modified pig manure carbon is more suitable for planting crops. The original soil pH is acid soil, the pH of the ordinary pig manure carbon is only improved by 7% after application, and the pH of the in-situ nitrogen-doped magnetically-modified pig manure carbon prepared in the embodiment 1 of the invention is improved by 19.3% after application, so that the acidification of the soil is effectively relieved. After the in-situ nitrogen-doped magnetically-modified pig manure carbon prepared in the embodiment 1 of the invention is applied, the organic matter content of the soil is improved by 24.9%, and the fertility of the soil is effectively increased. In addition, the yield of crops is obviously increased by applying the in-situ nitrogen-doped magnetically-modified pig manure carbon, the amplitude of the yield can reach 21.4%, and the yield of the ordinary pig manure carbon is only increased by 7.1%.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.
Claims (10)
1. A preparation method of in-situ nitrogen-doped magnetically-modified pig manure carbon is characterized by comprising the following steps:
(1) Mixing the dry pig manure powder and the water hyacinth powder, adding an adhesive and deionized water for hydrothermal carbonization, filtering and drying to obtain nitrogen-doped hydrothermal carbon;
(2) And mixing the nitrogen-doped hydrothermal carbon with typha orientalis root powder, and then carrying out high-temperature pyrolysis carbonization to obtain the in-situ nitrogen-doped magnetically-modified pig manure carbon.
2. The method for preparing the in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 1, wherein the method for preparing the dry pig manure powder in the step (1) comprises the following steps: dehydrating, pickling, drying and crushing pig manure to obtain dry pig manure powder;
the preparation method of the water hyacinth powder comprises the following steps: cleaning, crushing and drying the water hyacinth to obtain water hyacinth powder;
the preparation method of the cattail root powder comprises the following steps: cleaning, crushing and drying the cattail root to obtain cattail root powder.
3. The method for preparing in-situ nitrogen-doped magnetically modified pig manure carbon according to claim 2, wherein the dehydration is: dehydrating the pig manure until the water content is 80-85%;
the pickling solution adopted by the pickling is H 3 PO 4 Solution or HNO 3 The concentration of the pickling solution is 1-3mol/L;
the drying temperature of the pig manure is 85-100 ℃, and the drying time is 12-20h;
the crushing comprises the following steps: pulverizing to particle size of less than 0.1mm;
the drying temperature of the water hyacinth and the cattail root is 90-105 ℃, and the water hyacinth and the cattail root are dried until the water content is 0%; the powder is crushed into powder and is sieved by a 100-mesh sieve.
4. The method for preparing the in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 1, wherein the mass ratio of the dry pig manure powder to the water hyacinth powder in the step (1) is 1: (2.5-4); the adhesive is NaSO 4 And the addition amount is 0.5 to 1.5 percent of the sum of the dry pig manure powder and the water hyacinth powder; the addition amount of the deionized water is 60-90mL.
5. The method for preparing in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 1, wherein in the step (1), the hydrothermal carbonization is as follows: reacting for 18-24h under the conditions that the heating rate is less than or equal to 5 ℃/min and the temperature is 180-250 ℃;
the drying temperature is 85-100 ℃, and the drying time is 24h.
6. The method for preparing in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 1, wherein the mass ratio of the nitrogen-doped hydrothermal carbon to the cattail root powder in the step (2) is 4: (1-2);
before the high-temperature pyrolysis, 100-200mL of 1-3mol/L hydrochloric acid solution is firstly put into the high-temperature pyrolysis reactor to be uniformly dispersed, and then the high-temperature pyrolysis reactor is dried for 60-120min at the temperature of 85-100 ℃ and is added with N 2 Is high-temperature pyrolysis carbonization in the environment of protective gas.
7. The method for preparing in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 6, wherein the high-temperature pyrolysis carbonization is as follows: heating to 400-600 deg.C at a heating rate of 10-15 deg.C/min, and sealing for 2-5h.
8. The method for preparing in-situ nitrogen-doped magnetically-modified pig manure carbon according to claim 1, wherein after the high-temperature pyrolysis carbonization in the step (2), the obtained substance is added into 100-200mL of 1-3mol/L NaOH solution, the solution is kept at 80 ℃ for 2-4h, and then is washed with deionized water and dried at 85-100 ℃ for 24h.
9. An in-situ nitrogen-doped magnetically-modified pig manure carbon prepared by the preparation method of the in-situ nitrogen-doped magnetically-modified pig manure carbon as claimed in any one of claims 1 to 8.
10. Use of the in situ nitrogen-doped magnetically modified pig manure carbon of claim 9 in soil improvement.
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| CN110171830A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of preparation method and applications of N doping magnetic bio charcoal |
| CN113023707A (en) * | 2021-03-26 | 2021-06-25 | 深圳金普迈生物科技有限公司 | Preparation method of modified biochar for improving heavy metal pollution |
| CN113120898A (en) * | 2021-05-20 | 2021-07-16 | 四川大学 | Nitrogen-doped formed biochar and preparation method and application thereof |
| US20230148315A1 (en) * | 2020-04-20 | 2023-05-11 | Zhejiang University Of Science And Technology | Special pig manure charcoal modified by amino grafting, preparation method thereof, and its application in the reuse of nitrogen from farmland drainage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110171830A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of preparation method and applications of N doping magnetic bio charcoal |
| US20230148315A1 (en) * | 2020-04-20 | 2023-05-11 | Zhejiang University Of Science And Technology | Special pig manure charcoal modified by amino grafting, preparation method thereof, and its application in the reuse of nitrogen from farmland drainage |
| CN113023707A (en) * | 2021-03-26 | 2021-06-25 | 深圳金普迈生物科技有限公司 | Preparation method of modified biochar for improving heavy metal pollution |
| CN113120898A (en) * | 2021-05-20 | 2021-07-16 | 四川大学 | Nitrogen-doped formed biochar and preparation method and application thereof |
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