Heat patch filling material - SDES co-modified biochar, preparation method and application

Abstract

This invention discloses a heat patch liner-SDES co-modified biochar, its preparation method, and its application. First, a switch-type eutectic solvent is prepared. Then, the switch-type eutectic solvent is mixed with hollyhock stalk powder and heat patch liner powder, followed by high-temperature pyrolysis in a tube furnace to obtain modified biochar. The heat patch liner and hollyhock stalk biochar raw materials used are both waste materials, making them inexpensive and readily available, reducing resource waste. The prepared modified biochar can be reused, achieving the effect of "treating waste with waste." Furthermore, the prepared switch-type eutectic solvent is a novel CO2 switch-type green solvent, characterized by simple preparation, low melting point, non-toxicity, and biodegradability, further enhancing the performance of the biochar and enabling it to effectively remove pollutants from water and remediate heavy metal-contaminated soil.

Description

Technical Field

[0001] This invention belongs to the field of modified biochar preparation technology, and relates to a heat patch inner material - SDES co-modified biochar, preparation method and application. Background Technology

[0002] With the rapid development of the economy and society, human production activities have increasingly polluted the environment. The overuse of antibiotics in the aquaculture industry and the substandard discharge of various industrial wastewaters have led to a large amount of pollutants such as heavy metals, antibiotics, and dyes directly entering the environment, causing the water and soil environment to deteriorate continuously.

[0003] In recent years, biochar has attracted widespread attention due to its high specific surface area, large pore structure, and abundant oxygen-containing functional groups. Biochar has been widely used in environmental remediation, but the effect of raw biochar in removing pollutants is not ideal. Modification of biochar can improve its pollutant removal efficiency. There are many modification methods for biochar, such as acid-base modification, magnetic modification, and organic-inorganic hybridization. However, these methods are usually expensive, have complex preparation processes, and can cause secondary pollution during application.

[0004] Eutectic solvents have attracted widespread attention as a novel type of green solvent. They are produced by mixing hydrogen bond acceptors and hydrogen bond donors in a certain proportion, resulting in a solvent with a melting point lower than that of any single component. They offer significant advantages such as low preparation cost, non-toxicity, and biodegradability. Currently, eutectic solvents are widely used in the separation and extraction of substances, but their research and application in modified biochar are still relatively limited.

[0005] Hollyhocks are plants belonging to the Malvaceae family and the Althaea genus. Their roots can be used medicinally. They commonly grow in grassy areas, along ditches, and field edges. However, due to their large yield, much of them is carelessly discarded and not utilized properly, resulting in a waste of biomass resources. Heat packs, as a heating material, are increasingly used. Their inner material is a mixture of iron, vermiculite, activated carbon, water, etc. Because they are inexpensive, people dispose of them like ordinary garbage after use, causing not only environmental pollution but also wasting usable resources. Summary of the Invention

[0006] The purpose of this invention is to solve the problems in the prior art and provide a heat patch inner material - SDES co-modified biochar, its preparation method and application.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] A method for preparing SDES co-modified biochar as a heat patch filling material includes the following steps:

[0009] Metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol were mixed and then heated in an oil bath to obtain a switchable eutectic solvent.

[0010] The mixture is obtained by mixing hollyhock stalk powder, heat patch inner material powder and switch-type eutectic solvent, and then heating and stirring.

[0011] The mixture was placed in a tube furnace, and nitrogen gas was introduced into the furnace. After heating and carbonization, modified biochar was obtained.

[0012] A further improvement of the present invention is that:

[0013] The molar ratio of metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol is 1:1:4.

[0014] The mass ratio of the hollyhock stalk powder, the heat pack inner material powder, and the switch-type eutectic solvent is 2:1:9.

[0015] Metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol were mixed and heated to 100°C for 30 minutes.

[0016] The hollyhock stalk powder and the heat patch inner material powder need to be dried before mixing. The drying temperature is 105℃ and the drying time is 48 hours.

[0017] The hollyhock stalk powder, the heat patch inner material powder, and the switch-type eutectic solvent are mixed and heated to a temperature of 70-90℃ for 2-5 hours.

[0018] During the carbonization process, the heating rate is 10℃ / min, the carbonization temperature is 500-700℃, and the time is 2 hours.

[0019] A type of heat patch inner material - SDES co-modified biochar, which is prepared using any of the preparation methods of the present invention.

[0020] The application of SDES co-modified biochar, the inner material of the heat patch as described in this invention, in water pollution treatment.

[0021] The application of SDES co-modified biochar, the inner material of the heat patch as described in this invention, in the remediation of soil contaminated with heavy metals.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention discloses a method for preparing SDES-modified biochar from heat patch lining material. First, a switch-type eutectic solvent is prepared. Then, the switch-type eutectic solvent is mixed with hollyhock stalk powder and heat patch lining material powder to obtain modified biochar. The heat patch lining material and hollyhock stalk biochar raw materials used are both waste materials, making them inexpensive and readily available, reducing resource waste. The prepared modified biochar can be reused, achieving the effect of "treating waste with waste." Furthermore, the obtained switch-type eutectic solvent is a novel CO2 switch-type green solvent, characterized by simple preparation, low melting point, non-toxicity, and biodegradability, further enhancing the performance of the biochar and enabling it to effectively remove pollutants from water and remediate heavy metal-contaminated soil.

[0024] This invention discloses a heat patch inner material - SDES co-modified biochar. The modified biochar is prepared using waste raw materials, which reduces resource waste and achieves the effect of "treating waste with waste". Moreover, the modified biochar of this invention can be used for the removal of various water pollutants and the remediation of heavy metal contaminated soil with good removal effect, and has broad application prospects.

[0025] This invention discloses the application of SDES co-modified biochar as a heat patch filling material in water pollution treatment. It has good adsorption performance for pollutants in water bodies and can effectively adsorb heavy metals, dyes and antibiotics in both single and complex systems.

[0026] This invention discloses the application of SDES co-modified biochar in the remediation of heavy metal contaminated soil. Adding the modified biochar obtained by this invention to contaminated soil not only has a good passivation ability for heavy metals in the soil, but also improves the pH value, electrical conductivity, organic matter and other values ​​of the soil, enhances enzyme activity, and has a good effect on improving the physical and chemical properties of the soil. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is a schematic diagram of the preparation method of the present invention. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0030] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0031] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0032] In the description of the embodiments of the present invention, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. Furthermore, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0033] Furthermore, the use of the term "horizontal" does not imply that the component must be absolutely horizontal, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0034] In the description of the embodiments of the present invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in the present invention according to the specific circumstances.

[0035] The present invention will now be described in further detail with reference to the accompanying drawings:

[0036] See Figure 1 This invention discloses a method for preparing a heat patch inner material-SDES co-modified biochar, specifically: a method for preparing a heat patch inner material and a switch-type eutectic solvent co-modified biochar, where SDES represents a switch-type eutectic solvent.

[0037] Includes the following steps:

[0038] Step 1: Mix metformin hydrochloride, ammonium pentaborate tetrahydrate and glycerol in a certain proportion and heat in an oil bath to obtain a switch-type eutectic solvent.

[0039] Step 2: Dry, pulverize, and sieve the heat patch filling material to obtain heat patch filling powder. Wash, dry, pulverize, and sieve the hollyhock stems to obtain hollyhock stem powder.

[0040] Step 3: Mix the switch-type eutectic solvent prepared in Step 1 with the heat patch inner material powder and hollyhock stalk powder obtained in Step 2 in a certain proportion and heat and stir.

[0041] Step 4: Place the obtained mixture in a tube furnace, introduce N2, and heat to carbonize to obtain the inner material of the heat pack and the switch-type eutectic solvent co-modified biochar.

[0042] Furthermore, in step 1, the molar ratio of metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol is 1:1:4.

[0043] Furthermore, metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol were mixed and heated to 100°C for 30 minutes.

[0044] Furthermore, the hollyhock stalk powder and the heat patch inner material powder need to be dried before mixing. The drying temperature is 105°C and the drying time is 48 hours. After drying, they are placed in a pulverizer for pulverization and passed through a 100-mesh sieve.

[0045] Furthermore, in step 2, the mass ratio of hollyhock stalk powder, heat patch inner material powder, and switch-type eutectic solvent is 2:1:9.

[0046] Furthermore, in step 3, the hollyhock stalk powder, the heat patch inner material powder, and the switch-type eutectic solvent are mixed and heated at 80°C for 5 hours.

[0047] Furthermore, in step 4, the heating rate is 10℃ / min, the carbonization temperature is 600℃, and the time is 2 hours.

[0048] Furthermore, in step 4, the heating rate is 10℃ / min, the carbonization temperature is 600℃, and the time is 2 hours.

[0049] The switchable eutectic solvent prepared in this embodiment of the invention is a novel CO2 switchable green solvent, which has the characteristics of simple preparation, low melting point, non-toxicity, and biodegradability.

[0050] The heat patch filling material and hollyhock stalk biochar raw materials used in the embodiments of the present invention are both waste materials, which are inexpensive and readily available, reducing the waste of resources and realizing "treating waste with waste".

[0051] The modified biochar prepared by the method provided in this invention can be used for the removal of various water pollutants and the remediation of heavy metal contaminated soil, and has good removal effect, showing broad application prospects.

[0052] This invention also discloses the application of the prepared heat patch inner material and the switch-type eutectic solvent co-modified biochar in water pollution treatment:

[0053] Example 1

[0054] Rifampin in water was adsorbed using biochar co-modified with heat patch inner material and switch-type eutectic solvent.

[0055] Add 0.1 g of the prepared modified biochar to 100 mL of a rifampicin solution with a concentration of 150 mg / L. Place the above adsorption system at room temperature and 400 rpm / min, and take samples at 0 min, 3 min, 5 min, 10 min, 20 min, 30 min, 45 min, 60 min, 90 min, 150 min, 180 min, 210 min, 240 min, 270 min, and 300 min, respectively. Filter the samples through a 0.45 μm aqueous filter membrane and measure the absorbance at 475 nm using a UV spectrophotometer.

[0056] Example 2

[0057] Rifampin in water was adsorbed using biochar co-modified with heat patch inner material and switch-type eutectic solvent.

[0058] The difference between this embodiment and Embodiment 1 is that the rifampicin concentration in this embodiment is 50 mg / L, while the other steps are the same.

[0059] Example 3

[0060] Rifampin in water was adsorbed using biochar co-modified with heat patch inner material and switch-type eutectic solvent.

[0061] The difference between this embodiment and Embodiment 1 is that the rifampicin concentration in this embodiment is 100 mg / L, while the other steps are the same.

[0062] Example 4

[0063] The adsorption of Congo red in water was achieved by using the inner material of a heat patch and a switch-type eutectic solvent to co-modify biochar.

[0064] The difference between this embodiment and Example 1 is that in this embodiment, Congo red solution is adsorbed, the concentration of Congo red solution is 150 mg / L, and its absorbance is measured at 500 nm using a UV spectrophotometer. All other steps are the same.

[0065] Example 5

[0066] The adsorption of Congo red in water was achieved by using the inner material of a heat patch and a switch-type eutectic solvent to co-modify biochar.

[0067] The difference between this embodiment and Example 1 is that in this embodiment, Congo red solution is adsorbed, the concentration of Congo red solution is 50 mg / L, and its absorbance value is measured at 500 nm using a UV spectrophotometer. All other steps are the same.

[0068] Example 6

[0069] Using heat patch inner material and switch-type eutectic solvent co-modified biochar to adsorb Cr in water 6+ .

[0070] The difference between this embodiment and Embodiment 1 is that this embodiment adsorbs Cr. 6+ Cr 6+ The concentration is 100 mg / L.

[0071] The sample was filtered through a 0.22 μm aqueous filter membrane and measured using an atomic absorption spectrometer; all other steps were the same.

[0072] Example 7

[0073] Using heat patch inner material and switch-type eutectic solvent co-modified biochar to adsorb Pb in water 2+ .

[0074] The difference between this embodiment and Embodiment 1 is that this embodiment adsorbs Pb. 2+ Pb 2+ The concentration was 100 mg / L, and all other steps were the same.

[0075] Example 8

[0076] Adsorption of Cd in water using heat patch inner material and switch-type eutectic solvent-modified biochar. 2+ .

[0077] The difference between this embodiment and Embodiment 1 is that this embodiment adsorbs Cd. 2+ Cd 2+ The concentration was 50 mg / L, and the remaining steps were the same.

[0078] Example 9

[0079] Using heat patch inner material and switch-type eutectic solvent co-modified biochar to adsorb Cr in water 6+ Pb 2+ Cd 2+ .

[0080] The difference between this embodiment and Embodiment 1 is that this embodiment adsorbs Cr. 6+ Pb 2+ Cd 2+ Cr 6+ The concentration is 100 mg / L, Pb 2+ The concentration is 100 mg / L, Cd 2+ The concentration was 50 mg / L, and the remaining steps were the same.

[0081] Table 1. Adsorption capacity and removal rate of pollutants in water by modified biochar

[0082]

[0083] As shown in the table above, the prepared modified biochar has good adsorption performance for pollutants in water bodies, and can effectively adsorb heavy metals, dyes and antibiotics in both single and complex systems.

[0084] This invention has a good adsorption effect on pollutants in water bodies, and can effectively remediate soil contaminated with chromium, cadmium and lead, and has a good soil improvement effect, thus having high practicality.

[0085] This invention also discloses the application of the prepared heat patch inner material and the switch-type eutectic solvent co-modified biochar in the remediation of heavy metal contaminated soil:

[0086] Example 10

[0087] Biochar modified with heat patch inner material and switch-type eutectic solvent was used to remediate Cr, Pb, and Cd heavy metal contaminated soil.

[0088] The prepared modified biochar was added to the contaminated soil at a ratio of 1.5%, and deionized water was added. The soil was then incubated at room temperature. The pH, conductivity, organic matter, cation exchange capacity, dehydrogenase activity, sucrase activity, urease activity, and the available contents of Cr, Pb, and Cd were compared at 0, 14, 34, 54, and 82 days.

[0089] Comparative Example 1

[0090] The difference between this comparative example and Example 10 is that the biochar added in this comparative example is the inner material of a heat patch, and the unmodified hollyhock stalk biochar is a switch-type eutectic solvent. The other steps are the same.

[0091] Table 2 Modified biochar for remediation of heavy metal contaminated soil

[0092]

[0093] In the table above, ① represents the results of Example 10, and ② represents the results of Comparative Example 1.

[0094] As shown in the table above, adding modified biochar to polluted soil not only has a good passivation ability for heavy metals in the soil, reducing the available states of Cr, Pb, and Cd by 121.962, 124.700, and 10.560 mg / kg after 82 days, but also increases the pH, electrical conductivity, organic matter, and other values ​​in the soil, enhances enzyme activity, and has a good effect on improving the physical and chemical properties of the soil.

[0095] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing SDES co-modified biochar as a heat patch inner material, characterized in that, Includes the following steps: Metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol were mixed and then heated in an oil bath to obtain a switchable eutectic solvent. The mixture is obtained by mixing hollyhock stalk powder, heat patch inner material powder and switch-type eutectic solvent, and then heating and stirring. The mixture was placed in a tube furnace, and nitrogen gas was introduced into the tube furnace. After heating and carbonization, modified biochar was obtained. The molar ratio of metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol is 1:1:4; The hollyhock stalk powder and the heat patch inner material powder need to be dried before mixing. The drying temperature is 105 ℃ and the drying time is 48 hours. The mixture of hollyhock stalk powder, heat patch inner material powder, and switch-type eutectic solvent is heated to a temperature of 70-90 ℃ for 2-5 hours.

2. The method for preparing SDES co-modified biochar as a heat patch inner material according to claim 1, characterized in that, The mass ratio of the hollyhock stalk powder, the heat pack inner material powder, and the switch-type eutectic solvent is 2:1:

9.

3. The method for preparing SDES co-modified biochar for heat patch lining according to claim 1, characterized in that, Metformin hydrochloride, ammonium pentaborate tetrahydrate, and glycerol were mixed and heated to 100°C for 30 minutes.

4. The method for preparing SDES co-modified biochar for heat patch lining according to claim 1, characterized in that, During the carbonization process, the heating rate is 10 °C / min, the carbonization temperature is 500-700 °C, and the time is 2 hours.

5. A heat patch inner material - SDES co-modified biochar, characterized in that, Prepared using any one of the preparation methods of claims 1 to 4.

6. The application of the SDES co-modified biochar inner material of the heat patch as described in claim 5 in water pollution treatment.

7. The application of the SDES co-modified biochar inner material of the heat patch as described in claim 5 in the remediation of heavy metal contaminated soil.

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