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    • 专利摘要:
    The present disclosure is related to the field of biochar materials, and in particular to a graphene-modified biochar and a method for making the same as well as the use thereof. The graphene-modified biochar comprises biochar and graphene complexed with the 5 biochar. The graphene is present in an amount of 1 to 3 wt. % with respect to a total amount of the graphene-modified biochar. The modification of biochar with graphene leads to an increase in phenomenon of agglomeration on biochar surfaces, and the modified biochar, after being applied to saline-alkaline soil, enables electrical conductivity, and water and organic matter contents of the soil and thus available 10 potassium and phosphorus and alkali-hydrolyzable nitrogen contents thereof to be enhanced, and thus enables available nutrient contents of the soil to be increased.
    公开号:NL2028146A
    申请号:NL2028146
    申请日:2021-05-05
    公开日:2021-07-30
    发明作者:Liu Jun；Wang Fangli
    申请人:Univ Qingdao Agricultural；
    IPC主号:
    专利说明:

    GRAPHENE-MODIFIED BIOCHAR AND METHOD FOR MAKING SAME AS
    WELL AS USE THEREOF Technical Field The present disclosure is related to the field of biochar materials, and in particular to a graphene-modified biochar and a method for making the same as well as the use thereof. Background Saline-alkali soil, also known as salty soil, is harmful to plants. As the society advances, the demand for a healthy, high-quality soil has become higher. However, the improper use of soil has caused large amounts of soil to become salty. Hence, it is urgent to solve the problem of soil salinization. Biochar is a carbon-rich organic material that is produced by pyrolysis of biomass in the absence of oxygen, and is widely used around the world. Biochar contains elemental carbon in abundance, and has a great number of micropores, a strong adsorption capacity, a huge specific surface area, a large amount of functional groups on surfaces, and a large diameter. Studies have shown that biochar has a beneficial effect in remediation of saline-alkali soil. Summary In view of the above problems, an objective of the present disclosure is to provide a graphene-modified biochar and a method for making the same as well as the use thereof, the graphene-modified biochar, after being applied to saline-alkali soil, enabling water content, water-retaining and infiltration capabilities, electrical conductivity, and air permeability of the soil and thus the nutrient content thereof to be enhanced, and thus realizing remediation or improvement of the saline-alkali soil. One objective of the disclosure is realized by a graphene-modified biochar, comprising biochar and graphene complexed with the biochar, wherein the graphene is present in an amount of 1 to 3 wt. % with respect to a total amount of the graphene-modified biochar. The graphene component preferably has a diameter of 0.2 to 50 um and a thickness of
    0.7 to 4 nm. Moreover, the graphene preferably has a carbon content equal to or more than 97.09 wt. %.
    The biochar component preferably has a volumetric weight of 0.5 to 0.55 g/m’, a pH value of 6.8 to 7.1, and a carbon content of 75 to 78 wt. %.
    Further, the biochar is preferably produced by carbonization of Palmoxylon.
    Another objective of the disclosure is realized by a method for making the graphene- modified biochar as described above, comprising steps of: mixing biochar with graphene in a mass ratio of 97-99:0.5-2.2 to form a mixture; and subjecting the mixture to a calcination process so as to obtain a graphene-modified biochar.
    The calcination process preferably comprises a low-temperature calcination process and then a high-temperature calcination process.
    Preferably, the low-temperature calcination process is carried out at a temperature of 97 to 103 °C for 0.8 to 1.2 hours. Preferably, the high-temperature calcination process is carried out at a temperature of 495 to 505 °C for 0.5 to 0.6 hours.
    Further, the calcination process is preferably conducted in the absence of oxygen.
    Yet another objective of the disclosure is realized by the use of the graphene-modified biochar as described above or of a graphene-modified biochar made according to the method as described above in soil improvement, which is performed by applying the graphene-modified biochar to the soil to be treated, with an amount of 0.1 to 0.3 wt. % with respect to a total amount of the graphene-modified biochar and the soil.
    Preferably, the graphene-modified biochar is applied to the soil with a depth of 0 to 20 cm.
    As described above, the present disclosure provides a graphene-modified biochar, which comprises biochar and graphene complexed with the biochar. The graphene is present in an amount of 1 to 3 wt. % with respect to the total amount of the graphene-modified biochar. It has been found that, the modification of biochar with graphene leads to an increase in phenomenon of agglomeration on biochar surfaces, and the modified biochar, after being applied to saline-alkaline soil, enables electrical conductivity, and water and organic matter contents of the soil and thus available potassium (K) and phosphorus (P) and alkali-hydrolyzable nitrogen (N) contents thereof to be enhanced, and thus enables available nutrient contents of the soil to be increased.
    The present disclosure further provides a method for making the graphene-modified biochar as described above, comprising: mixing biochar with graphene in a mass ratio of 97-99:0.5-2.2 to form a mixture; and subjecting the mixture to a calcination process so as to obtain a graphene-modified biochar. According to the method, graphene is complexed with biochar by calcination to give a graphene-modified biochar. The method is simple and easy to implement, and is suitable for industrial production. Brief Description of the Drawings FIG. 1 shows a system, used in Example 1, for performing a soil infiltration process. Detailed Description A first aspect of the disclosure provides a graphene-modified biochar, comprising biochar and graphene complexed with the biochar. The graphene is present in an amount of 1 to 3 wt. % with respect to a total amount of the graphene-modified biochar. In an embodiment, the biochar is produced by carbonization of Palmoxylon. The carbonization is preferably conducted at a temperature of 450 to 550 °C, more preferably at 500 to 520 °C, for 210 to 330 minutes, more preferably for 240 to 300 minutes. The biochar component preferably has a volumetric weight of 0.5 to 0.55 g/m’, more preferably 0.51 to 0.53 g/m’, a pH value of 7.8 to 8, more preferably 7.85 to 7.89, and a carbon content of 75 to 78 wt. %, more preferably 76 to 77 wt. %. The graphene preferably has a diameter of 0.2 to 50 um, more preferably 0.5 to 30 um. Moreover, the graphene preferably has a thickness of 0.7 to 4 nm, more preferably 0.8 to 3.6 nm. Further, the graphene preferably has a carbon content equal to or greater than
    97.09 wt. %, more preferably of 98 to 99.9 wt. %. In this description, the graphene used was purchased from SHANDONG JINCHENG GRAPHENE TECHNOLOGY Co, Ltd. It has been found that, modification of biochar with graphene leads to an increase in phenomenon of agglomeration on biochar surfaces, and the modified biochar, after being applied to saline-alkaline soil, enables electrical conductivity, and water and organic matter contents of the soil and thus available K and P and alkali-hydrolyzable N contents thereof to be enhanced, and thus enables available nutrient contents of the soil to be increased. A second aspect of the disclosure provides a method for making the graphene-modified biochar as described above, comprising: mixing biochar with graphene in a mass ratio of 97-99:0.5-2.2 to form a mixture; and subjecting the mixture to a calcination process so as to obtain a graphene-modified biochar.
    According to the method, biochar is mixed with graphene in a mass ratio of 97-99:0.5-
    2.2, preferably 98:2. The mixing process is not particularly limited as long as a uniform mixing of biochar and graphene is ensured.
    In an embodiment, the calcination process comprises a low-temperature calcination process and then a high-temperature calcination process. The low-temperature calcination process is preferably conducted at a temperature of 97 to 103 °C, more preferably 98 to 100 °C, for 0.8 to 1.2 hours, more preferably 0.9 to 1 hours. The high- temperature calcination process is preferably conducted at a temperature of 495 to 505 °C, more preferably 499 to 501 °C, for 0.5 to 0.6 hours, more preferably 0.53 to 0.55 hours. The high temperature, at which the high-temperature calcination process is conducted, is preferably reached by raising the low temperature at which the low- temperature calcination process is conducted. However, the temperature rising rate is not particularly limited herein.
    In an embodiment, the calcination process is conducted in the absence of oxygen. In a further embodiment, the mixture of biochar and graphene is placed in a stainless steel reactor, which is then evacuated. The reactor may be evacuated to any pressure as long as the air inside the reactor is removed. Further, the calcination device is not particularly limited as long as it is adapted to conduct the calcination process as described above. In an embodiment, a muffle furnace is employed for the calcination process.
    After the calcination process, the graphene is bound onto surfaces of the biochar. Preferably, the method further comprises a cooling process performed after the calcination process. Through the cooling process, the graphene-modified biochar is preferably cooled to room temperature. The cooling process may be performed in any manner as long as the required temperature is achieved.
    A third aspect of the disclosure provides the use of the graphene-modified biochar as described above or of a graphene-modified biochar made according to the method as described above in soil improvement, which is performed by applying the graphene- modified biochar to the soil to be treated, with an amount of 0.1 to 0.3 wt. % with respect to a total amount of the graphene-modified biochar and the soil.
    In an embodiment, the soil to be treated is saline-alkaline soil. The graphene-modified biochar is added to the soil to be treated in an amount of 0.1 to 0.3 wt. %, preferably
    0.15 to 0.2 wt. %, with respect to a total amount of the graphene-modified biochar and the soil. The mass percentage of the graphene-modified biochar applied to the soil to be treated with respect to the total amount of the graphene-modified biochar and the soil is preferably obtained in accordance with the following equation I: biochar soil (Equation I), where, Msoi (mass of the soil to be treated) represents the mass of surface soil, which 5 preferably has a depth of 0 to 20 cm, more preferably 10 to 15 cm.
    Further, after application of the graphene-modified biochar, it is preferably mixed with the surface soil.
    This mixing process is not particularly limited, and any manner well known to those skilled in the art may be used.
    To illustrate the effects of the graphene-modified biochar of the present disclosure, saline-alkaline soil in Maotuo village, Dongying city, Shandong Province was sampled.
    Preparation of the soil sample preferably comprises steps of: collecting surface soil with a depth of 0 to 20 cm using a shovel; subjecting the collected surface soil to impurity removal and then air drying so as to obtain dried soil; and subjecting the dried soil to be pulverized and sieved to obtain a soil sample.
    The impurity removal step is preferably intended to remove large and hard particles present in the surface soil, such as rocks.
    The collected surface soil is air dried to constant weight and the time is not particularly limited herein.
    Further, the air drying step is preferably performed in a shadowy place, and should not be exposed to direct insolation by sunlight.
    The pulverization preferably takes place via grinding.
    The sieving step is preferably performed by using a screen having an opening diameter of 1 nm.
    After preparation of the soil sample, its physicochemical properties were analyzed by using a MS-2000 laser particle size analyzer.
    The results are shown in Table 1. Table 1 Physicochemical properties of the soil sample ci Satin, Volmetris Total Sin Organic Available nutrients sample PE Ae oy For content co EE ’ mgee) Nmghgy dmgho sain T88 ass 152 $23 372 839 317 18 151.5 The disclosure will now be described in further detail by way of the following examples, however, which should not be construed as limiting the scope of the disclosure.
    Example 1 Palmoxylon was carbonized at 550 °C for 5 h to obtain a biochar product, which had a volumetric weight of 0.51 g/m*, a pH value of 7.89, and a carbon content of 76.48 wt. %. The biochar was washed until the pH of the wash water was neutral.
    99 g of biochar was mixed with 1 g of graphene having a particle size of 20 um, a thickness of 1.2 nm, and a carbon content of 98 wt. %, and was then transferred into a stainless steel reactor. The reactor was evacuated and placed into a muffle furnace. The mixture inside the muffle furnace was calcined at 100 °C for 1 h, and was then heated from 100 °C to 500 °C. This temperature was maintained for 0.5 h. Thereafter, the IO mixture was cooled down to room temperature along with the furnace. A graphene- modified biochar was then obtained. Example 2 Palmoxylon was carbonized at 550 °C for 5 h to obtain a biochar product, which had a volumetric weight of 0.51 g/m’, a pH value of 7.89, and a carbon content of 76.48 wt. %. The biochar was washed until the pH of the wash water was neutral. 100 g of biochar was mixed with 1 g of graphene having a particle size of 14 um, a thickness of 2 nm, and a carbon content of 97.9 wt. %, and was then transferred into a stainless steel reactor. The reactor was evacuated and placed into a muffle furnace. The mixture inside the muffle furnace was calcined at 100 °C for 1 h, and was then heated from 100 °C to 500 °C. This temperature was maintained for 0.5 h. Thereafter, the mixture was cooled down to room temperature along with the furnace. A graphene- modified biochar was then obtained. Test Example The graphene-modified biochar in Example 1 was mixed with the soil sample in different mixing ratios to prepare soil test samples having a biochar content of 0, 0.1 wt. %, 0.15 wt. %, and 0.3 wt. %, denoted as BC, B1, B2, and B3, respectively. Measurement of soil water content A bottom opening of an organic glass tube (with an inner diameter of 5 cm and a height of 30 cm) of a Mariotte bottle was closed with a =40 mesh nylon net to prevent loss of the soil test sample to be filled thereinto and to facilitate venting. Vaseline was evenly applied to an inner surface of the organic glass tube to reduce the influence of the inner surface on a subsequent infiltration process. Quartz sand was filled onto an upper surface of the nylon net inside the tube in a height of 2 cm in order to ensure air permeability of the soil test sample to be filled thereinto.
    Each of the soil test samples prepared above was filled into the tube in layers with each layer having a height of 2 cm. After filling the tube with each single layer, its weight was measured, until all layers had been filled into the tube. During this, an upper surface of each single layer, which was expected to come in contact with one layer that would be filled onto it next, was roughened to ensure close contact between the layers and to IO prevent delamination during a subsequent infiltration process. After the filling had been completed, a piece of filter paper was placed on an exposed upper surface of the soil test sample inside the tube to prevent the surface to be scoured by a liquid supplied to the tube. Thereafter, a top opening of the tube was closed with a =40 mesh nylon net. The tube was then fixed to a stand. A soil infiltration column was thus obtained.
    From the left to the right in FIG. 1, a container containing a liquid for soil infiltration, a peristaltic pump, the soil infiltration column, and a sampling bottle were connected. In this example, 0.01 mol/L of calcium chloride (CaCl) aqueous solution (simulated rainwater) was used as the liquid to be supplied to the soil infiltration column, and the sampling bottle was a conical flask.
    Infiltration characteristics of the soil test samples were measured through one- dimensional vertical infiltration. At the beginning, the peristaltic pump drew the liquid in the container such that the liquid was added to the column at a rate of 0.02 ml per minute, with a distance between the liquid outlet and the upper surface of the test sample inside the tube kept at around 1 cm. After the filter paper was completely water wet, timing began. Movement of the wetting front, which was an interface between the wet part of and the dry part of the soil test sample formed during the infiltration process, was observed while the recording operation was being performed. When the wetting front reached the bottom of the column, the addition of the liquid was stopped.
    The experiments were repeated 3 times, and the results were averaged.
    The soil inside the tube was then sampled at different depths, with each sample having a weight of 15 g. These samples were separately placed into an aluminum box having a weight of M; and then weighed, and the weight was denoted as Wi. The aluminum box was then placed in a drying oven at 105 °C along with the sample therein to be dried to constant weight.
    Now, their weight (the weight of both the aluminum box and the sample therein) was measured and denoted as Wa.
    The water content 9 of the samples was calculated by the following formula I.
    The results are shown in Table 2. WW, b= 21 "100% W, — M, Formula I Table 2 Change in soil water content with depth of the soil BC Bl B2 BI Water | Water Water Water Depth Depth Depth Depth content | content content / content fom fhe fom icm 9% 0% 1% a a 42.3 i FF12 & 46.51 0 $2.44 5 31.14 5 3243 5 32734 5 3712 16 2882 1 29.96 1D 3115 18 36.81 15 28.69 £5 30 16 13 303.06 15 37.02 20 2873 26 30.04 0 303.09 26 36 66 25 2841 25 29.85 2% LIS 25 34.67 30 24 68 30 22.34 30 2434 38 28.55 In a case in which the soil water content is excessively low or excessively high, there is a problem in that growth of soil micro-organisms and of vegetation roots is adversely influenced.
    In particular, if the soil water content is excessively high, it is detrimental to respiration of the organisms; while if the soil water content is excessively low, it may fail to meet the expected water needs of the organisms.
    It can be seen from Table 2 that, the soil water content decreased with an increase in the depth of the soil, and a distinct transition occurred at the depth of around 5 and 25 cm.
    Further, the soil water content remained substantially constant within the depth of 5 to 25 cm.
    It can also be seen from Table 2 that, after the graphene-modified biochar of the present disclosure was applied to the saline-alkaline soil, the soil water content and water retention capacity were improved.
    Measurement of soil electric conductivity The soil inside the tube was sampled at different depths, and each sample was leached with pure water to obtain leaching liquids.
    An electrical conductivity meter was used to measure the electrical conductivity of the liquids.
    The results are shown in Table 3.
    Table 3 Change 1 soul electrical conductivity with depth of the nil BC Bl B2 B3 Depth Conductivity Depth Conductivity Depth Conductivity Depth Conductivity Jem Sp Cm a fom {Og fom Va
    0.3 A 03 3 {32 5 0.34 in 035 id 0.3% i 4.45 in 0.43 15 3.583 is LINS is {1.55 15 0.64 2% 135 20 1.53 26 1.79 20 1.3% 25 598 25 6.34 25 £45 25 547 Soil electrical conductivity is the ability of soil particles and ions to conduct electricity. It can generally reflect soil fertility conditions, and can be used to further estimate soil saline content. It can be seen from Table 3 that, for the soil test samples of BC, B1, B2, 5 and B3, the soil electrical conductivity increased with an increase in the depth of the soil, but the soil electrical conductivity of the samples of B1, B2, and B3 increased more than that of the sample BC. Measurement of organic matter content in soil The organic matter content of the soil test samples of BC, B1, B2, and B3 were measured by a Total Organic Carbon (TOC) analyzer. The results are shown in Table 4. Table 4 Organic matter content in soil Sample 33 Soil organic matter is an important component of soil and sediments, and is the basis of soil fertility. It can be seen from Table 4 that, as compared with the bland control sample BC, the organic matter contents of the soil test samples of B1, B2, and B3 increased by 25 %, 32.14 %, and 60.71 %, respectively. Measurement of available nutrients in soil After sieving the soil test samples of BC, BI, B2, and B3 through a 1.0 mm screen, available K and P and alkali-hydrolyzable N contents in the samples were measured according to NY/T 889-2004, GB 12297-1990, and LY/T 1229-1999. The results are shown in Table 5.
    Table 5 Available nutrient contents in soil Available K 7% 143 1504 1334 134.8 Available P; 8 iis 1251 17.0% 2118 alkal-hydrolyzable N/ % 33.17 35.39 37.25 49.09 It can be seen from Table 5 that, after the graphene-modified biochar of the present disclosure was applied to the saline-alkaline soil, the available K and P and alkali- hydrolyzable N contents therein were increased. In particular, as compared with the bland control sample BC, the available K contents in the soil test samples of B1, B2, and B3 increased by 1.07 %, 2.28 %, and 3.89 %, respectively; the available P contents in the soil test samples of B1, B2, and B3 increased by 8.49 %, 43.11 %, and 77.98 %, respectively; and the alkali-hydrolyzable N contents in the soil test samples of B1, B2, and B3 increased by 6.69 %, 12.42 %, and 48.00 %, respectively.
    Ithas been found that, the graphene-modified biochar of the present disclosure can cause an increase in phenomenon of agglomeration on biochar surfaces, and after being applied to saline-alkaline soil, enables electrical conductivity, and water and organic matter contents of the soil and thus the available K and P and alkali-hydrolyzable N contents thereof to be enhanced, and thus enables the available nutrient contents of the soil to be increased.
    The present disclosure has been described with reference to specific embodiments. However, it is clear that the described embodiments are only a part, but not all, of the embodiments of the disclosure. Other embodiments can be conceived by those skilled in the art based on the described embodiments, and shall fall within the scope of the disclosure as defined by the appended claims.
    权利要求:
    Claims (10)
    [1]
    A graphene-modified biocoal comprising biocoal and graphene complexing with the biocoal, wherein the graphene is present in an amount of 1 to 3% by weight with respect to a total amount of the graphene-modified biocoal.
    [2]
    The graphene-modified biochar of claim 1, wherein the graphene has a diameter of 0.2-50 µm, a thickness of 0.7-4 nm and a carbon content equal to or greater than 97.09 % by weight.
    [3]
    The graphene-modified biocoal of claim 1, wherein the biocoal component has a volumetric weight of 0.5 - 0.55 g/m 2 , a pH of 6.8 - 7.1 and a carbon content of 75 - 78 by weight. % has.
    [4]
    The graphene-modified biocoal according to claim 1 or 3, wherein the biocoal is produced by carbonization of Palmoxylon.
    [5]
    A method for manufacturing the graphene-modified bio-coal according to any one of claims 1 to 4, wherein the method comprises the steps of: mixing the bio-coal with graphene in a mass ratio of 97 -99 : 0.5 -2, 2 to form a mixture; and subjecting the mixture to a calcination process to obtain the graphene-modified biochar.
    [6]
    The method of claim 5, wherein the calcination process comprises a low temperature calcination process and then a high temperature calcination process.
    [7]
    The method of claim 6, wherein the low temperature calcination process is conducted at a temperature of 97 - 103°C for 0.8 - 1.2 hours, and wherein the high temperature calcination process is conducted at a temperature of 495 - 505°C for 0.5 — 0.6 hours.
    S12 -
    [8]
    A method according to any one of claims 5 to 7, wherein the calcination process is performed in the absence of oxygen.
    [9]
    Use of the graphene-modified biocoal according to any one of claims 1 to 4 or a graphene-modified biocoal produced by the method according to any of claims 5 to 8 in soil improvement, which is carried out by applying the graphene modified bio-coal on the earth to be treated, in an amount of 0.1 - 0.3 % by weight with respect to a total amount of the graphene-modified bio-coal and the earth.
    [10]
    Use according to claim 9, wherein the graphene-modified bio-coal is applied to the soil with a depth of 0-20 cm.
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