CN111676025B - Humic acid embedded biochar-nano hydroxyapatite composite material and preparation method and application thereof - Google Patents
Humic acid embedded biochar-nano hydroxyapatite composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional soil improvement, and particularly relates to a humic acid embedded biochar-nano hydroxyapatite composite material, a preparation method and application thereof; firstly, drying and heating straws to prepare biochar, then carrying out surface modification on the biochar by using nano-hydroxyapatite prepared by a chemical precipitation method, and finally embedding the modified material by using a sodium humate solution to finally prepare the composite functional material of humic acid embedded biochar-nano-hydroxyapatite. According to the invention, the rice straw biochar is used as a core material, the input of available phosphorus is increased through the modification of nano-hydroxyapatite, the adsorption quantity of the biochar to sodium humate is increased, and the problem of low effective phosphorus increase caused by the independent application of the biochar in the low organic matter content sandy soil is solved.
Description
Technical Field
The invention belongs to the technical field of functional soil improvement, and particularly relates to a humic acid embedded biochar-nano hydroxyapatite composite material, and a preparation method and application thereof.
Background
At present, the desertification area of the land of 261.16 ten thousand square kilometers in China occupies about one fourth of the area of the land of China, so that the problem of how to prevent desertification and actively developing and utilizing aeolian sandy soil resources is the issue of striking attention. The aeolian sandy soil has low organic matter content, low available phosphorus content and great difficulty in plant planting and survival. In order to protect and improve the agricultural ecological environment and maintain the sustainable development of agriculture in northwest arid and semiarid sandy soil areas, a functional material is needed to be prepared, so that the effectiveness and the soil fertility of phosphorus in soil are improved, proper soil conditions are created, the water and fertilizer supply capacity of the soil is coordinated, and the soil quality of sandy soil is improved.
The biochar is a highly aromatic refractory solid carbon-rich substance produced by pyrolysis of biomass under the anoxic condition. The biochar has the advantages of rich pore structure, large specific surface area, high biochemical stability and strong adsorption performance, and plays an important role in increasing the reserve of a soil carbon reservoir, improving the soil quality, retaining soil nutrients, improving the crop yield and the like. As a novel functional material input from an external source, the biochar directly or indirectly participates in phosphorus circulation in a soil ecosystem and has certain influence on the conversion process of phosphorus substances in the soil.
Soil pH is one of the major limiting factors in effective phosphorus enhancement during biochar application. In acid soil, the effectiveness of soil phosphorus can be improved by applying the biochar; however, in alkaline soil, the physical and chemical properties of the biochar can cause the pH value of the soil to be continuously increased, and the effective phosphorus in the soil is low in synergism.
Disclosure of Invention
In order to solve the technical problems, the invention provides a humic acid embedded biochar-nano hydroxyapatite composite material, a preparation method and application thereof.
The invention aims to provide a preparation method of a humic acid embedded biochar-nano hydroxyapatite composite material, which comprises the following steps:
preparing biochar: cleaning and drying farmland biomass straws, crushing the farmland biomass straws, carbonizing the farmland biomass straws by a carbonization furnace, and finally grinding and sieving the farmland biomass straws to obtain a biochar material;
preparing nano hydroxyapatite: preparing 2.36-2.37 g/100mL calcium nitrate tetrahydrate solution with the pH value of 10 and 0.79-0.80 g/100mL diammonium phosphate solution with the pH value of 10; slowly and dropwise adding a diammonium hydrogen phosphate solution into a calcium nitrate tetrahydrate solution, keeping the temperature of a reaction system at 40-50 ℃, stirring for 30-60 min, then continuing aging for 12-14 h, washing, precipitating and drying to obtain nano hydroxyapatite;
preparing biochar-nano hydroxyapatite: mixing nano hydroxyapatite with deionized water according to the weight ratio of 0.5g: mixing the materials in a proportion of 100mL, and then adding biochar into the solution; stirring, mixing, washing, precipitating and drying to obtain biochar-nano hydroxyapatite material;
preparing a humic acid embedded biochar-nano hydroxyapatite composite material: preparing a sodium humate solution of 200mg/L, pH 6; mixing the biochar-nano hydroxyapatite material with a sodium humate solution, oscillating and mixing for 2-3 d, centrifuging, filtering, washing the precipitate, and drying the precipitate to obtain the humic acid embedded biochar-nano hydroxyapatite composite material.
Preferably, in the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material, the farmland biomass straws are rice straws, sorghum straws, corn straws or wheat straws.
Preferably, the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material comprises the following carbonization conditions: the temperature is 450 ℃, and the carbonization time is 1 h; naturally cooling to 60 ℃ after carbonization, and then taking out the biochar material.
Preferably, in the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material, the molar ratio of Ca to P is 1.67:1 when nano hydroxyapatite is prepared.
Preferably, the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material comprises the following steps of: the mass ratio of the nano hydroxyapatite is 1: 1.
Preferably, in the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material, the biochar-nano hydroxyapatite is prepared by stirring and mixing for 24 hours.
Preferably, in the preparation method of the humic acid-embedded biochar-nano hydroxyapatite composite material, when the humic acid-embedded biochar-nano hydroxyapatite composite material is prepared, the ratio of the biochar-nano hydroxyapatite material to a sodium humate solution is 0.5g to 50 mL.
The second purpose of the invention is to provide a humic acid embedded biochar-nano hydroxyapatite composite material prepared by the method.
The third purpose of the invention is to provide the application of the humic acid embedded biochar-nano hydroxyapatite composite material as or in the preparation of a sandy soil remediation agent.
Preferably, the humic acid embedded biochar-nano hydroxyapatite composite material and the sand blown by the wind to be repaired are mixed according to the mass ratio of 1-5: 100.
Compared with the prior art, the preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material provided by the invention has the following beneficial effects:
humic Acid (HA) is one of important components in soluble organic matters, HAs complex components and numerous functional groups including carboxyl, hydroxyl, phenol group and alcohol group, and plays a key role in phosphorus adsorption and analysis with the special group and an acid organism. In addition, the humic acid can relieve the increase of the pH value of the soil caused by the biochar, and the problem that the application of the biochar to alkaline soil is limited by the influence of the pH value can be improved by embedding the biochar by the humic acid. According to the invention, sodium humate is embedded in the modified charcoal, so that the pH value of the aeolian sandy soil is reduced by 0.04-0.21. The original unmodified biochar material has a small humic acid adsorption amount (the adsorption amount of the unmodified biochar on sodium humate is only 13% w/w obtained through experiments), and the actual effect of the biochar applied to the low organic matter content aeolian sandy soil can be influenced.
Nano hydroxyapatite (Ca)10(PO4)6(OH)2HAP) is a calcium phosphate biological material, has a unique structure and has the characteristics of strong adsorption capacity, acid-base adjustability, ion exchange capacity, good thermal stability and the like. In addition, HAP is used as a novel phosphate fertilizer, the application of the HAP has obvious effect of improving the effective phosphorus content of soil, and the use amount of the phosphate fertilizer can be saved and reduced.
According to the invention, the biological carbon and the nano-hydroxyapatite are applied in a combined manner, so that not only can the stability of the nano-hydroxyapatite be enhanced, but also the specific surface area and the pore volume of the biological carbon can be increased, and thus the overall adsorbability of the composite material is improved. According to the invention, the specific surface area of the biochar is increased by 4.69-8.18 times by modifying the biochar through the nano-hydroxyapatite, and the adsorption (80%, w/w) of the modified biochar to sodium humate is further increased.
According to the invention, rice straw biochar is taken as a core material, the biochar is modified by an intermediate medium nano-hydroxyapatite and a humic acid embedding technology, so that the adsorption quantity of the biochar to sodium humate is increased, the contribution capacity of a composite material to soil available phosphorus is improved, and the problem of low synergistic effect of the biochar available phosphorus when independently applied to low organic matter content aeolian sandy soil is solved. The material preparation cost is low, and the method is simple and convenient.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) micrograph of a biochar-nano hydroxyapatite and humic acid embedded biochar-nano hydroxyapatite composite;
a. b is the photograph of HAP-FRBC under different scales, c, d are the photographs of HAP-FRBC-HANa under different scales, e, f are the photographs of HAP-RBC under different scales, g, h are the photographs of HAP-RBC-HANa under different scales;
FIG. 2 is a Scanning Electron Microscope (SEM) micrograph of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material;
a is a photograph of HAP-FRBC, b is a photograph of HAP-FRBC-HANa, c is a photograph of HAP-RBC, and d is a photograph of HAP-RBC-HANa;
FIG. 3 is an X-ray energy spectrum diffraction (EDS) of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material;
a is a graph of HAP-FRBC, b is a graph of HAP-FRBC-HANA, c is a graph of HAP-RBC, and d is a graph of HAP-RBC-HANA;
FIG. 4 is an X-ray diffraction pattern (XRD) of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material;
FIG. 5 is a Fourier transform infrared (FT-IR) spectrum of a biochar-nano hydroxyapatite and humic acid embedded biochar-nano hydroxyapatite composite;
in FIGS. 4 to 5, a is a graph of HAP, HAP-RBC, and HAP-FRBC, b is a graph of HANa, HAP-RBC, and HAP-RBC-HANa, and c is a graph of HANa, HAP-FRBC, and HAP-FRBC-HANa.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention to be implemented, the present invention will be further described with reference to the following specific embodiments and accompanying drawings. The following examples, as well as test methods not specifically identified in the summary of the invention, were conducted according to methods and conditions conventional in the art.
Example 1
The preparation method of the humic acid embedded biochar-nano hydroxyapatite composite material comprises the following steps
(1) Preparing biochar: the biochar raw material is prepared from farmland biomass rice straws, is cleaned by tap water, is air-dried, is crushed to be about 2cm in length, and is put into a plastic bag for later use. The rice straw is treated at high temperature by a carbonization furnace (convenient biomass carbonization machine for combined research and development of Huaian Hua electric environmental protection machinery manufacturing Co., Ltd., Nanjing agriculture university) with the set temperature of 450 ℃ and the carbonization time of 1 h. And opening a charcoal outlet valve when the temperature is naturally cooled to 60 ℃, and collecting the biochar material. Grinding the biochar and then sieving the biochar by a 10-mesh sieve or a 200-mesh sieve; when the biomass is sieved by a 10-mesh sieve (ground into particles with the particle size of about 10 meshes), the coarse-particle biochar is marked as RBC, and when the biomass is sieved by a 200-mesh sieve (ground into particles with the particle size of about 200 meshes), the fine-particle biochar is marked as FRBC.
(2) Preparing nano hydroxyapatite: firstly, accurately weighing 4.723g of calcium nitrate tetrahydrate, dissolving in 200mL of deionized water, uniformly mixing, and adjusting the pH value of the solution to 10 by using sodium hydroxide; then, 1.584g of diammonium phosphate is weighed, dissolved in 200mL of deionized water, and the pH value is adjusted to 10 by using sodium hydroxide; finally, slowly and dropwise adding a diammonium hydrogen phosphate solution into a calcium nitrate tetrahydrate solution, wherein the molar ratio of Ca to P is 1.67:1, the temperature of a reaction system is always kept at 40 ℃, the pH value of the solution is kept at about 10, and the solution is white. After stirring for 30min, aging is continued for 12 h. Washing the precipitate with deionized water for 3 times, and drying at 65 deg.C to obtain nano hydroxyapatite labeled HAP.
(3) Preparing biochar-nano hydroxyapatite: firstly, accurately weighing 2g of HAP, placing the HAP in a 1000mL big beaker, adding 400mL of deionized water, placing the beaker on a magnetic stirrer, adjusting the rotation speed to 800rpm, and fully and uniformly mixing the HAP for 30 min. According to the biological carbon: and (2) slowly adding 2g of the biological carbon into a HAP solution system according to the mass ratio of 1:1, reducing the rotating speed to 500rpm, continuously stirring for 24h, washing the precipitation material for 3 times by using deionized water, and drying in a 65 ℃ drying oven (DGX-9143B, manufactured by Shanghai Zhicheng analytical instruments Co., Ltd.) to obtain the biological carbon-nano hydroxyapatite material. When the added biochar is RBC, the coarse particle modified biochar is marked as HAP-RBC; when the added biochar is FRBC, the fine particle modified biochar is marked as HAP-FRBC.
(4) Preparing a humic acid embedded biochar-nano hydroxyapatite composite material: firstly, 200mg of sodium humate is weighed, dissolved in 1000mL of deionized water, and filtered through a 0.45-micron filter membrane, and the pH value is adjusted to 6 by HCl, so that 200mg/L of humic acid solution is obtained for later use. Secondly, 0.5g of biochar-nano hydroxyapatite is taken into a 50mL centrifuge tube, and 50mL of sodium humate solution is added. A control group was set by adding 50mL of deionized water (without humic acid). Placing the centrifuge tube on a double-layer large-capacity shaking table (Shanghai Nanrong, model NRY-2012C), and performing shake culture at room temperature for 2 d. The tube was removed and placed in a centrifuge (Saimer Feishell science, USA, model ST16R), centrifuged at 5000rpm for 5min, the precipitate was washed 1 time with 50mL of deionized water, the filtrates were filtered through 0.45 μm filters, and about 100mL of the total filtrate was collected. And (3) measuring Total Organic Carbon (TOC) in the filtrate by using an Shimadzu TOC-LCPH analyzer, and calculating that the maximum embedding amount of humic acid reaches 80 percent and w/w. And (3) drying the precipitate material in a drying oven at 65 ℃ to obtain the humic acid embedded biochar-nano hydroxyapatite composite material, wherein the coarse particle composite material is marked as HAP-RBC-HANa, and the fine particle composite material is marked as HAP-FRBC-HANa.
Analyzing the specific surface area (BET) of the biochar-nano hydroxyapatite material obtained in the step 3, wherein the specific surface areas of RBC, FRBC, HAP-RBC and HAP-FRBC are 2.219m2/g，5.619m2/g，18.142m2G and 26.337m2The volume of the pore diameter is 0.006cm3/g，0.017cm3/g，0.068cm3G and 0.117cm3(ii)/g; the modification of the nano hydroxyapatite can be seen to improve the specific surface area and the pore size of the biochar, so that the absorption of the sodium humate is facilitated, and the humic acid embedded biochar-nano hydroxyapatite composite material is obtained after the step (4). The resulting composite was characterized.
FIG. 1 is a Transmission Electron Microscope (TEM) micrograph of a biochar-nano hydroxyapatite and humic acid embedded biochar-nano hydroxyapatite composite; a. b is the photograph of HAP-FRBC under different scales, c, d are the photographs of HAP-FRBC-HANa under different scales, e, f are the photographs of HAP-RBC under different scales, g, h are the photographs of HAP-RBC-HANa under different scales. In fig. 1, the black sheet-shaped matter is biochar, the rice grain-shaped matter is nano hydroxyapatite, and the nano hydroxyapatite can be successfully loaded on the biochar from the graphs a, b, e and f; the grey black floccule is sodium humate, and the sodium humate can be seen from figures c, d, g and h to successfully embed the modified biochar.
FIG. 2 is a Scanning Electron Microscope (SEM) micrograph of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material; a is a photograph of HAP-FRBC, b is a photograph of HAP-FRBC-HANa, c is a photograph of HAP-RBC, and d is a photograph of HAP-RBC-HANa. The layered and porous lumps are biochar, the rice grains are nano hydroxyapatite, and the nano hydroxyapatite can be successfully loaded on the biochar as shown in the figures a and c; the graphs b and d show that the nano hydroxyapatite has agglomeration phenomenon and the edge seems to have a layer substance, and the sodium humate successfully embeds the modified biochar.
FIG. 3 is an X-ray energy spectrum diffraction (EDS) of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material; a is a graph of HAP-FRBC, b is a graph of HAP-FRBC-HANA, c is a graph of HAP-RBC, and d is a graph of HAP-RBC-HANA; the obvious characteristic peaks of phosphorus and calcium elements can be seen from the graphs a and c, which indicates that the nano hydroxyapatite is successfully loaded on the biochar; the characteristic peaks of the nano element and the characteristic peaks of the carbon-oxygen element can be seen in the graphs b and d, which shows that the sodium humate successfully embeds the modified biochar.
FIG. 4 is an X-ray diffraction pattern (XRD) of a biochar-nano-hydroxyapatite and humic acid embedded biochar-nano-hydroxyapatite composite material; a is graph of HAP, HAP-RBC, and HAP-FRBC, b is graph of HANa, HAP-RBC, and HAP-RBC-HANa, and c is graph of HANa, HAP-FRBC, and HAP-FRBC-HANa. From the figure a, a characteristic diffraction peak which is coincident with the nano-hydroxyapatite appears on the biochar, which shows that the nano-hydroxyapatite is successfully loaded on the biochar; and the characteristic diffraction peaks of the modified biochar coincident with the sodium humate can be seen in the graphs b and c, which shows that the sodium humate successfully embeds the modified biochar.
FIG. 5 is a Fourier transform infrared (FT-IR) spectrum of a biochar-nano hydroxyapatite and humic acid embedded biochar-nano hydroxyapatite composite; a is graph of HAP, HAP-RBC, and HAP-FRBC, b is graph of HANa, HAP-RBC, and HAP-RBC-HANa, and c is graph of HANa, HAP-FRBC, and HAP-FRBC-HANa. From the figure a, a characteristic absorption peak which is coincident with the nano-hydroxyapatite appears on the biochar, which shows that the nano-hydroxyapatite is successfully loaded on the biochar; and b.c, a characteristic absorption peak of the modified biochar which is overlapped with the sodium humate can be seen, which shows that the sodium humate successfully embeds the modified biochar.
As can be seen from a transmission electron microscope, a scanning electron microscope, an energy spectrum diffraction pattern, an X-ray diffraction pattern and a Fourier infrared spectrum, the nano-hydroxyapatite successfully modifies the biochar and successfully adsorbs sodium humate to obtain the humic acid embedded biochar-nano-hydroxyapatite composite material.
Example 2
The composite material obtained by the invention is used for improving the aeolian sandy soil with low available phosphorus and low organic matters, and the specific implementation steps are as follows:
a preparation method of a humic acid embedded biochar-nano hydroxyapatite composite material comprises the following steps:
(1) preparing biochar: the biochar raw material is prepared from farmland biomass rice straws, is cleaned by tap water, is air-dried, is crushed to be about 2cm in length, and is put into a plastic bag for later use. The rice straw is treated at high temperature by a carbonization furnace (convenient biomass carbonization machine for combined research and development of Huaian Hua electric environmental protection machinery manufacturing Co., Ltd., Nanjing agriculture university) with the set temperature of 450 ℃ and the carbonization time of 1 h. And opening a charcoal outlet valve when the temperature is naturally cooled to 60 ℃, and collecting the biochar material. The charcoal was ground and passed through a 10 mesh screen and labeled as RBC.
(2) Preparing nano hydroxyapatite: firstly, accurately weighing 4.723g of calcium nitrate tetrahydrate, dissolving in 200mL of deionized water, uniformly mixing, and adjusting the pH value of the solution to 10 by using sodium hydroxide; then, 1.584g of diammonium phosphate is weighed, dissolved in 200mL of deionized water, and the pH value is adjusted to 10 by using sodium hydroxide; finally, slowly and dropwise adding a diammonium hydrogen phosphate solution into a calcium nitrate solution, wherein the molar ratio of Ca to P is 1.67:1, the temperature of the reaction system is always kept at 50 ℃, the pH value of the solution is kept at 10, and the solution is white. After stirring for 30min, aging is continued for 12 h. Washing the precipitate with deionized water for 4 times, and drying at 65 ℃ to obtain the nano hydroxyapatite marked as HAP.
(3) Preparing biochar-nano hydroxyapatite: firstly, accurately weighing 2g of HAP, placing the HAP in a 1000mL big beaker, adding 400mL of deionized water, placing the beaker on a magnetic stirrer, adjusting the rotation speed to 800rpm, and fully and uniformly mixing the HAP for 30 min. According to the biological carbon: and (2) slowly adding 2g of biochar into an HAP solution system according to the mass ratio of 1:1, reducing the rotating speed to 500rpm, continuously stirring for 24h, washing the precipitation material with deionized water for 4 times, and drying at 65 ℃ (DGX-9143B, a model of Shanghai Zhicheng analytical instrument manufacturing Limited company) to obtain the modified biochar of the biochar-nano hydroxyapatite material, namely HAP-RBC.
(4) Preparing a humic acid embedded biochar-nano hydroxyapatite composite material: firstly, 200mg of humic acid sodium salt is weighed, dissolved in 1000mL of deionized water, and filtered through a 0.45-micron filter membrane, and the pH value is adjusted to 6 by HCl, so that 200mg/L humic acid solution is obtained for standby. Secondly, 0.5g of biochar-nano hydroxyapatite is taken into a 50mL centrifuge tube, and 50mL of sodium humate solution is added. A control group was set by adding 50mL of deionized water (without humic acid). Placing the centrifuge tube on a double-layer large-capacity shaking table (Shanghai Nanrong, model NRY-2012C), and performing shake culture at room temperature for 3 d. The tube was removed and placed in a centrifuge (Saimer Feishell science, USA, model ST16R), centrifuged for 5min at 5000rpm, the precipitate was washed 1 time with deionized water, the filtrates were filtered through 0.45 μm filters, and about 100mL of the total filtrate was collected. The Total Organic Carbon (TOC) in the filtrate was determined by Shimadzu TOC-LCPH analyzer, and the maximum embedding amount of humic acid was calculated to reach 80% (w/w). And (3) drying the precipitate material in a drying oven at 65 ℃ to obtain the humic acid embedded biochar-nano hydroxyapatite composite material which is marked as HAP-RBC-HANa.
(5) The obtained biochar and humic acid embedded biochar-nano hydroxyapatite composite material is tested, and the test is as follows:
test soil: ningxia sandy soil. The basic physical and chemical properties of the soil are as follows: the water content is 14.5 percent, the pH value is 9.49, the total phosphorus is 0.16g/kg, the available phosphorus is 15.45mg/kg, and the organic matter is 2.20 g/kg.
A total of 5 treatments were tested: 1) a control group, a blank soil without any biochar material; 2) applying low-concentration biochar into soil, wherein the using amount is 1g/100 g; 3) applying high-concentration biochar in the soil, wherein the using amount is 5g/100 g; 4) applying low-concentration humic acid embedded biochar-nano hydroxyapatite composite material into soil, wherein the dosage is 1g/100 g; 5) high-concentration humic acid embedded biochar-nano hydroxyapatite composite material is applied to soil, and the dosage is 5g/100 g.
The test is carried out in a soil culture experiment of 100 days in an artificial climate chamber (the temperature is 25 ℃, the humidity is 50-58% and under the dark condition), deionized water is added to the treated soil every 2 days during the culture period, the water content of the soil is maintained at 65% of the maximum water holding capacity, the uniformly mixed soil is harvested after the test is finished, and the main physicochemical properties of the soil are tested, wherein the results are shown in table 1.
TABLE 1 physicochemical properties of soil for improving aeolian sandy soil
As can be seen from table 1, the application of the biochar and the biochar composite material can significantly increase the contents of total phosphorus and available phosphorus in the soil; compared with the method of independently applying the biochar material, the composite material has more remarkable increase of the content of the total phosphorus and the effective phosphorus in the soil due to the addition of the nano-hydroxyapatite modified material, and the treatment effect of the high-concentration composite material is most obvious; at the same time, the application of the composite material all caused a significant increase in the organic matter content of the soil. The composite material synthesized and prepared by the invention is used for improving the content of available phosphorus and organic matters in the aeolian sandy soil, and can achieve the final purpose of improving the soil fertility of the aeolian sandy soil.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A preparation method of humic acid embedded biochar-nano hydroxyapatite composite material is characterized by comprising the following steps:
preparing biochar: cleaning and drying farmland biomass straws, crushing the farmland biomass straws, carbonizing the farmland biomass straws by a carbonization furnace, and finally grinding and sieving the farmland biomass straws to obtain a biochar material; the farmland biomass straws are rice straws, sorghum straws, corn straws or wheat straws;
preparing nano hydroxyapatite: preparing 2.36-2.37 g/100mL calcium nitrate tetrahydrate solution with the pH value of 10 and 0.79-0.80 g/100mL diammonium phosphate solution with the pH value of 10; slowly and dropwise adding a diammonium hydrogen phosphate solution into a calcium nitrate tetrahydrate solution, keeping the temperature of a reaction system at 40-50 ℃, stirring for 30-60 min, then continuing aging for 12-14 h, washing, precipitating and drying to obtain nano hydroxyapatite;
preparing biochar-nano hydroxyapatite: mixing nano hydroxyapatite with deionized water according to the weight ratio of 0.5g: mixing the materials in a proportion of 100mL, and then adding biochar into the solution; stirring, mixing, washing, precipitating and drying to obtain biochar-nano hydroxyapatite material;
preparing a humic acid embedded biochar-nano hydroxyapatite composite material: preparing a sodium humate solution of 200mg/L, pH 6; mixing the biochar-nano hydroxyapatite material with a sodium humate solution, oscillating and mixing for 2-3 d, centrifuging, filtering, washing the precipitate, and drying the precipitate to obtain the humic acid embedded biochar-nano hydroxyapatite composite material.
2. The preparation method of humic acid embedded biochar-nano hydroxyapatite composite material according to claim 1, characterized in that the carbonization conditions are as follows: the temperature is 450 ℃, and the carbonization time is 1 h; naturally cooling to 60 ℃ after carbonization, and then taking out the biochar material.
3. The method for preparing humic acid embedded biochar-nano hydroxyapatite composite material according to claim 2, wherein the molar ratio of Ca to P is 1.67:1 when preparing nano hydroxyapatite.
4. The method for preparing the humic acid embedded biochar-nano hydroxyapatite composite material according to claim 3, wherein the biochar-nano hydroxyapatite is prepared according to the following steps of: the mass ratio of the nano hydroxyapatite is 1: 1.
5. The method for preparing the humic acid-embedded biochar-nano hydroxyapatite composite material according to claim 4, wherein the stirring and mixing time is 24 hours when the biochar-nano hydroxyapatite is prepared.
6. The method for preparing the humic acid-embedded biochar-nano hydroxyapatite composite material according to claim 4, wherein the ratio of the biochar-nano hydroxyapatite material to the sodium humate solution is 0.5g:50mL when the humic acid-embedded biochar-nano hydroxyapatite composite material is prepared.
7. A humic acid embedded biochar-nano hydroxyapatite composite material prepared by the method of any one of claims 1 to 6.
8. Use of the humic acid-embedded biochar-nano hydroxyapatite composite material as defined in claim 7 as or in the preparation of a sandy soil remediation agent.
9. The application of the humic acid-embedded biochar-nano hydroxyapatite composite material as a sandy soil remediation agent or in the preparation of a sandy soil remediation agent according to claim 8 is characterized in that the humic acid-embedded biochar-nano hydroxyapatite composite material is mixed with sandy soil to be remedied according to the mass ratio of 1-5: 100.
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