Preparation method of adsorbed berberine hydrochloride electrolytic manganese residue and coke composite material

Abstract

The application belongs to the field of adsorbing material preparation, and particularly relates to a method for synthesizing a magnetic porous high-efficiency adsorbing berberine hydrochloride electrolytic manganese residue and coke composite material by a two-step ball-milling pyrolysis method, which comprises the following steps: ball-milling electrolytic manganese residue to obtain manganese residue powder; crushing coke to obtain coke and drying; soaking the manganese residue powder in sulfuric acid to generate a manganese-iron salt solution; washing and then plasma-activating the coke; washing and then plasma-activating the manganese-iron salt solution; stirring the coke product and the manganese-iron salt solution product in a water bath; mixing the obtained product with acetic acid, then adding a mixed solution of trisodium citrate and oxalic acid dihydrate, and then plasma-activating; program heating and pyrolyzing the obtained product; washing and drying the obtained product, and the target product is obtained. The composite material can efficiently treat berberine hydrochloride in wastewater containing berberine hydrochloride, has strong adsorbing capacity, ideal material functionality, and is easy to recycle.

Description

Technical Field

[0001] This invention belongs to the field of adsorption material preparation, specifically relating to a method for synthesizing a magnetic porous high-efficiency adsorption material of berberine hydrochloride electrolytic manganese slag and coke using a two-step ball milling pyrolysis method. Background Technology

[0002] In recent years, pharmaceuticals and personal care products (PPCPs) have attracted widespread attention due to their strong polarity and biological activity, posing threats to ecosystems and human health. Berberine hydrochloride, used to treat cancer, diabetes, and liver diseases, is a typical anti-inflammatory drug. Wastewater from BH production is a typical pharmaceutical wastewater generated in the Liaohe River basin of China. The hazards of berberine hydrochloride-containing wastewater include: 1. Impact on ecosystems: berberine hydrochloride-containing wastewater disrupts microbial life, inhibits microbial reproduction, and leads to ecological imbalance; 2. Impact on crops: using berberine hydrochloride-containing wastewater for farmland irrigation not only leads to poor crop growth but also contaminates food, affecting food quality and safety; 3. Impact on human health: long-term exposure to berberine hydrochloride-containing wastewater can lead to the formation of drug resistance genes and cause acute or chronic poisoning, causing long-term effects on human health. Currently, there are various methods for removing berberine hydrochloride from water. Among them, biodegradation treatment requires a long time, while electrochemical methods have a low removal rate. The Fenton oxidation method readily achieves high removal efficiency of berberine hydrochloride, but the intermediate products of berberine hydrochloride conversion typically exhibit high biotoxicity. In contrast, adsorption methods overcome these drawbacks and have attracted widespread attention.

[0003] Manganese, a vital strategic resource in my country, is widely used in industries such as steel, chemicals, agriculture, high-end equipment manufacturing, new energy vehicles, and new materials. my country's manganese smelting primarily utilizes electrolysis, making it the world's largest producer, consumer, and exporter of electrolytic manganese. Due to limitations in extraction efficiency, producing 1 ton of electrolytic manganese generates 7-18 tons of electrolytic manganese slag, and my country's stockpiled slag exceeds 100 million tons. This slag accumulation not only occupies significant land resources, but also releases heavy metals such as manganese, cadmium, copper, zinc, lead, and chromium through surface runoff, rainwater leaching, and soaking, migrating into surrounding soil, water bodies, and vegetation. These slags can directly or indirectly harm human health through contact and the food chain. Therefore, applying electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) to adsorption applications can help conserve resources, improve economic efficiency, and reduce environmental pollution.

[0004] The porous structure of coke is an important component of its overall structure. The microcrystalline structure of coke is a densely packed, ordered layered structure, very similar to the crystal structure of graphite. This microcrystalline structure and porosity make coke an excellent adsorbent for berberine hydrochloride. Furthermore, since the main components of electrolytic manganese slag are manganese oxide and iron oxide, mixing it with coke and ball milling pyrolysis not only increases pore volume and specific surface area but also imbues the coke with magnetism, allowing it to be recovered from water after use. However, a common problem with single-metal modification is leaching, which can be harmful to the environment or affect the quality of treated water. Using bimetallic modification can improve the safety of coke and reduce metal leaching. After mixed pyrolysis, the iron and manganese in the electrolytic manganese slag are loaded onto the coke in the form of iron-manganese oxides, providing more active sites for the adsorption of berberine hydrochloride. Summary of the Invention

[0005] This invention aims to overcome the shortcomings of existing technologies by providing a simple and low-cost method for preparing a composite material of electrolytic manganese slag and coke that can efficiently remove berberine hydrochloride. This composite material can efficiently treat berberine hydrochloride in wastewater containing berberine hydrochloride, exhibits strong adsorption capacity in complex water bodies, demonstrates ideal material functionality, and is easily recyclable.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke is carried out according to the following steps:

[0008] (1) The dried electrolytic manganese slag is placed in a ball mill and ball-milled to obtain manganese slag powder;

[0009] (2) The coke is crushed using a grading crusher and screened using a standard sieve with a particle size range of 20 to 100 mesh to obtain coke;

[0010] (3) Place the coke obtained in step (2) into an oven and dry it;

[0011] (4) Soak the manganese slag powder obtained in step (1) in sulfuric acid to generate a manganese iron salt solution;

[0012] (5) The coke obtained in step (3) is washed with deionized water and then activated with O2 plasma;

[0013] (6) The manganese iron salt solution obtained in step (4) is washed with deionized water and then activated with O2 plasma;

[0014] (7) Stir the plasma-activated coke product obtained in step (5) and the plasma-activated manganese iron salt solution product obtained in step (6) in a water bath.

[0015] (8) Place the product obtained in step (7) into an oven and dry it;

[0016] (9) The product obtained in step (8) is mixed with acetic acid in a wet ball mill mixer;

[0017] (10) The product obtained in step (9) is added to a mixed solution of trisodium citrate and oxalic acid dihydrate, washed with deionized water, and then activated with O2 plasma.

[0018] (11) Place the product obtained in step (10) into an oven and dry it;

[0019] (12) Place the product obtained in step (11) into a quartz boat and place it in a tube furnace. Under N2 atmosphere, heat the product by program and pyrolyze it, then cool it to room temperature.

[0020] (13) Wash the product obtained in step (12) with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material, and dry it in an oven to obtain the target product.

[0021] Further, in step (1), the electrolytic manganese slag is placed in a 90°C oven and dried for 30 minutes; the dried electrolytic manganese slag is then placed in a ball mill with a ball gradation of 6:4:1, a ball-to-electrolytic manganese slag ratio of 3:1, and a rotation speed of 300 r / min and ball-milled for 1 hour to obtain manganese slag powder.

[0022] Further, in step (4), the manganese slag powder obtained in step (1) is soaked in a solution with a sulfuric acid concentration of 0.5-2.0 mol / L, a temperature of 60℃, and a solid-liquid ratio of 1:15 g / L for 1.0 h to generate a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0023] Further, in step (5), the coke obtained in step (3) is washed with deionized water and then activated with O2 plasma; the activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0024] Further, in step (6), the manganese iron salt solution obtained in step (4) is washed with deionized water and then activated with O2 plasma; the activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0025] Further, in step (7), the plasma-activated coke product obtained in step (5) and the plasma-activated manganese iron salt solution product obtained in step (6) are stirred in an 80°C water bath at a mass ratio of 3 to 1:1.

[0026] Further, in step (9), the dried product from step (8) is taken out and mixed with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer; the ball milling time is set to 2 h, the rotation speed is 300 r / min, and the experiment is stopped every 30 min to remove the gas in the ball mill tank.

[0027] Further, in step (10), the product obtained in step (9) is added to 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate, washed with deionized water, and then activated with O2 plasma. The activation time is set to 15 s, the flow rate to 100 sccm, the radio frequency power to 100 W, and the self-bias voltage to 300 V.

[0028] Further, in step (12), the product obtained in step (11) is placed in a quartz boat and placed in a tube furnace. Under N2 atmosphere, the temperature is raised to 500°C at a heating rate of 7°C / min and pyrolyzed for 2 hours, and then cooled to room temperature.

[0029] Further, in step (13), the pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the material surface, and then dried in an oven at 80°C for 12 hours to obtain the target product.

[0030] This invention employs a two-step ball milling pyrolysis process to synthesize a novel magnetic porous composite material of electrolytic manganese slag and coke, which exhibits excellent adsorption capacity for berberine hydrochloride, reaching a maximum adsorption capacity of 215 mg / g. The invention uses coke and electrolytic manganese slag as raw materials to prepare this novel magnetic porous composite material. The microcrystalline structure and porosity of coke make it an excellent adsorbent for berberine hydrochloride. After mixed pyrolysis, the iron and manganese in the electrolytic manganese slag are loaded onto the coke in the form of iron-manganese oxides, providing more active sites for berberine hydrochloride adsorption. Typically, berberine hydrochloride is removed as an H acceptor; the formation of iron-manganese oxides provides a good H donor for berberine hydrochloride removal. Adsorption experiments show that the composite material of electrolytic manganese slag and coke has excellent adsorption capacity for berberine hydrochloride. Using electrolytic manganese slag and coke as raw materials, a two-step ball milling pyrolysis process is employed to mix them. Plasma technology is then used to acid-activate the mixture, giving it better adsorption properties. This is an innovative attempt to address the problem of resource waste, solving not only the resource recycling issue but also the wastewater pollution problem caused by berberine hydrochloride production.

[0031] Since the main components of electrolytic manganese slag are manganese oxide and iron oxide, mixing it with coke and ball milling pyrolysis not only increases its pore volume and specific surface area but also imbues the coke with magnetism, allowing it to be recovered from water after use. However, a common problem with single-metal modification is leaching, which can be harmful to the environment or affect the quality of treated water. Using bimetallic modification can improve the safety of coke and reduce metal leaching. After mixed pyrolysis, the iron and manganese in the electrolytic manganese slag are loaded onto the coke in the form of iron-manganese oxides, providing more active sites for the adsorption of berberine hydrochloride. Plasma technology is used to activate the coke with acid, forming more active groups and pore structures conducive to berberine hydrochloride adsorption. Therefore, the mixing of electrolytic manganese slag and coke has advantages in improving adsorption performance and industrial applications. This invention uses electrolytic manganese slag and coke as raw materials, and employs a two-step ball milling pyrolysis method and acidic plasma activation technology to produce a magnetic porous composite material. This material can treat berberine hydrochloride production wastewater under various conditions, exhibiting strong adsorption capacity, a removal rate of over 90%, and easy recovery. Attached Figure Description

[0032] The present invention will now be described in detail through specific embodiments. These embodiments are provided to enable a more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art. As used throughout the specification and claims, the terms "comprising" or "including" are open-ended and are interpreted as "comprising but not limited to". The following description is a preferred embodiment for carrying out the invention; however, this description is intended to illustrate the general principles of the specification and is not intended to limit the scope of the invention. The scope of protection of the invention is determined by the appended claims. Unless otherwise specified, all reagents and materials used in the present invention are commercially available.

[0033] Figure 1 This is an adsorption diagram under different influencing factors according to the present invention;

[0034] Figure 2 This invention prepares a composite material of electrolytic manganese slag and coke;

[0035] Figure 3 SEM image of the electrolytic manganese slag and coke composite material prepared according to the present invention;

[0036] Figure 4 SEM image of the electrolytic manganese slag and coke composite material prepared according to the present invention;

[0037] Figure 5 The figure shows the effect of the electrolytic manganese slag and coke composite material prepared in this invention on the adsorption of berberine hydrochloride in complex water bodies with different ion presences.

[0038] Figure 6The figure shows the kinetics and mechanical properties of the adsorption of berberine hydrochloride on the composite material of electrolytic manganese slag and coke prepared in this invention.

[0039] Figure 7 Figure 1 shows the reusability study of the adsorption of berberine hydrochloride by the composite material of electrolytic manganese slag and coke prepared in this invention. Detailed Implementation

[0040] Example 1

[0041] A method for preparing a magnetic porous electrolytic manganese slag and coke composite material for adsorbing berberine hydrochloride includes the following steps:

[0042] (1) Place 10g of electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) in a 90℃ oven and dry for 30min. Place the dried manganese slag in a ball mill with a ball gradation of 6:4:1, a ball to manganese slag ratio of 1:1, and a rotation speed of 300r / min and ball mill for 1h to obtain manganese slag powder.

[0043] (2) The coke was crushed using a graded crusher and sieved using a standard sieve. Coke with a particle size of 40 mesh was selected as the sample.

[0044] (3) Place the coke obtained in step (2) into a 90℃ oven and dry for 30 minutes. After drying, pack it into bags for later use.

[0045] (4) Soak the manganese slag powder obtained in step (1) in 100 mL of 0.5 mol / L sulfuric acid solution at 60 °C with a solid-liquid ratio of 1:15 g / L for 1.0 h. The manganese oxide and iron oxide in the manganese slag dissolve out, and at the same time, the calcium, aluminum and other minerals in the manganese slag are removed, generating a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0046] (5) The coke powder with a particle size of 40 mesh obtained in step (3) is washed with deionized water and then activated with O2 plasma. The activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0047] (6) After washing with 0.5 mol / L sulfuric acid in step (4) to obtain a manganese-iron salt solution with a manganese-iron mass ratio of 1:1, the solution is washed with deionized water and then subjected to plasma activation using the method in step (5).

[0048] (7) The plasma-activated coke powder obtained in step (5) and the plasma-activated manganese iron salt solution obtained in step (6) are stirred in an 80°C water bath at a mass ratio of 1:1 until they are evenly dispersed and free of lumps.

[0049] (8) The uniformly dispersed coke and manganese iron salt mixture obtained in step (7) is dried in an oven at 90°C for 24 hours.

[0050] (9) Take out the dried product from step (8) and mix it with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer. Set the ball milling time to 2 h and the rotation speed to 300 r / min. Stop the experiment every 30 min. Expel the gas in the ball mill tank to prevent the generated gas from causing excessive pressure in the tank.

[0051] (10) Place the product obtained in step (9) into a beaker, add 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate (mass ratio 1:1), wash with deionized water, and then activate with O2 plasma. Set the activation time to 15 s, flow rate to 100 sccm, RF power to 100 W, and self-bias voltage to 300 V.

[0052] (11) Place the mixture of coke and manganese iron salt activated by mixed acid plasma in step (10) into an oven at 90°C and dry for 24 hours.

[0053] (12) Take out the dried mixture from step (11), put it in a quartz boat and place it in a tube furnace. Under N2 atmosphere, raise the temperature to 500°C at a heating rate of 7°C / min and pyrolyze for 2 hours, then cool to room temperature.

[0054] (13) The pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material. It is then dried in an oven at 90°C for 12 hours to obtain a magnetic porous electrolytic manganese slag and coke composite material that is Fe-Mn modified acid activated to facilitate the adsorption of berberine hydrochloride.

[0055] Example 2

[0056] A method for preparing a magnetic porous electrolytic manganese slag and coke composite material for adsorbing berberine hydrochloride includes the following steps:

[0057] (1) Place 10g of electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) in a 90℃ oven and dry for 30min. Place the dried manganese slag in a ball mill with a ball gradation of 6:4:1, a ball to manganese slag ratio of 2:1, and a rotation speed of 300r / min and ball mill for 1h to obtain manganese slag powder.

[0058] (2) The coke was crushed using a graded crusher and sieved using a standard sieve. Coke with a particle size of 60 mesh was selected as the sample.

[0059] (3) Place the coke in a 90℃ oven and dry for 30 minutes. After drying, pack it into bags for later use.

[0060] (4) The manganese slag powder obtained in step (1) is soaked in 100 mL of 1.0 mol / L sulfuric acid solution at 60 °C with a solid-liquid ratio of 1:15 g / L for 1.0 h. The manganese oxide and iron oxide in the manganese slag dissolve out, and at the same time, the calcium, aluminum and other minerals in the manganese slag are removed, generating a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0061] (5) The coke powder with a particle size of 60 mesh obtained in step (3) is washed with deionized water and then activated with O2 plasma. The activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0062] (6) The manganese-iron salt solution with a manganese-iron mass ratio of 1:1 generated by immersion in 1.0 mol / L sulfuric acid in step (4) is washed with deionized water and then subjected to plasma activation using the method in step (5).

[0063] (7) Stir the plasma-activated coke powder obtained in step (5) and the plasma-activated manganese iron salt solution obtained in step (6) in a mass ratio of 2:1 in an 80°C water bath until they are evenly dispersed and free of lumps.

[0064] (8) The resulting uniformly dispersed coke and manganese iron salt mixture was dried in an oven at 90°C for 24 hours.

[0065] (9) Take out the dried product from step (8) and mix it with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer. Set the ball milling time to 2 h and the rotation speed to 300 r / min. Stop the experiment every 30 min. Expel the gas in the ball mill tank to prevent the generated gas from causing excessive pressure in the tank.

[0066] (10) Place the product obtained in step (9) into a beaker, add 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate (mass ratio of 2:1), wash with deionized water, and then activate with O2 plasma. Set the activation time to 15 s, flow rate to 100 sccm, RF power to 100 W, and self-bias voltage to 300 V.

[0067] (11) Place the mixture of coke and manganese iron salt activated by mixed acid plasma in step (10) into an oven at 90°C and dry for 24 hours.

[0068] (12) Take out the dried mixture from step (11), put it in a quartz boat and place it in a tube furnace. Under N2 atmosphere, raise the temperature to 500°C at a heating rate of 7°C / min and pyrolyze for 2 hours, then cool to room temperature.

[0069] (13) The pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material. The product is then dried in an oven at 90°C for 12 hours to obtain a composite material of magnetic porous manganese slag and coke that is Fe-Mn modified by acid activation and is conducive to the adsorption of berberine hydrochloride.

[0070] Example 3

[0071] A method for preparing a magnetic porous electrolytic manganese slag and coke composite material for adsorbing berberine hydrochloride includes the following steps:

[0072] (1) Place 10g of electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) in a 90℃ oven and dry for 30min. Place the dried manganese slag in a ball mill with a ball gradation of 6:4:1, a ball to manganese slag ratio of 3:1, and a rotation speed of 300r / min and ball mill for 1h to obtain manganese slag powder.

[0073] (2) The coke was crushed using a graded crusher and sieved using a standard sieve. Coke with a particle size of 80 mesh was selected as the sample.

[0074] (3) Place the coke in a 90℃ oven and dry for 30 minutes. After drying, pack it into bags for later use.

[0075] (4) The manganese slag powder obtained in step (1) is soaked in 100 mL of 1.5 mol / L sulfuric acid solution at 60 °C with a solid-liquid ratio of 1:15 g / L for 1.0 h. The manganese oxide and iron oxide in the manganese slag dissolve out, and at the same time, the calcium, aluminum and other minerals in the manganese slag are removed, generating a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0076] (5) The coke powder with a particle size of 80 mesh obtained in step (3) is washed with deionized water and then activated with O2 plasma. The activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0077] (6) The manganese-iron salt solution with a manganese-iron mass ratio of 1:1 generated by immersion in 1.5 mol / L sulfuric acid in step (4) is washed with deionized water and then subjected to plasma activation using the method in step (5).

[0078] (7) Stir the plasma-activated coke powder obtained in step (5) and the plasma-activated manganese iron salt solution obtained in step (6) in a mass ratio of 3:1 in an 80°C water bath until they are evenly dispersed and free of lumps.

[0079] (8) The resulting uniformly dispersed coke and manganese iron salt mixture was dried in an oven at 90°C for 24 hours.

[0080] (9) Take out the dried product from step (8) and mix it with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer. Set the ball milling time to 2 h and the rotation speed to 300 r / min. Stop the experiment every 30 min. Expel the gas in the ball mill tank to prevent the generated gas from causing excessive pressure in the tank.

[0081] (10) Place the product obtained in step (9) into a beaker, add 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate (mass ratio of 3:1), wash with deionized water, and then activate with O2 plasma. Set the activation time to 15 s, flow rate to 100 sccm, RF power to 100 W, and self-bias voltage to 300 V.

[0082] (11) Place the mixture of coke and manganese iron salt activated by mixed acid plasma in step (10) into an oven at 90°C and dry for 24 hours.

[0083] (12) Take out the dried mixture from step (11), put it in a quartz boat and place it in a tube furnace. Under N2 atmosphere, raise the temperature to 500°C at a heating rate of 7°C / min and pyrolyze for 2 hours, then cool to room temperature.

[0084] (13) The pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material. It is then dried in an oven at 90°C for 12 hours to obtain a new composite material of magnetic porous manganese slag and coke that is Fe-Mn modified by acid activation and is conducive to the adsorption of berberine hydrochloride.

[0085] Example 4

[0086] A method for preparing a magnetic porous electrolytic manganese slag and coke composite material for adsorbing berberine hydrochloride includes the following steps:

[0087] (1) Place 10g of electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) in a 90℃ oven and dry for 30min. Place the dried manganese slag in a ball mill with a ball gradation of 6:4:1, a ball to manganese slag ratio of 4:1, and a rotation speed of 300r / min and ball mill for 1h to obtain manganese slag powder.

[0088] (2) The coke was crushed using a graded crusher and sieved using a standard sieve. Coke with a particle size of 100 mesh was selected as a sample.

[0089] (3) Place the coke in a 90℃ oven and dry for 30 minutes. After drying, pack it into bags for later use.

[0090] (4) The manganese slag powder obtained in step (1) is soaked in 100 mL of 2 mol / L sulfuric acid solution at 60 °C with a solid-liquid ratio of 1:15 g / L for 1.0 h. The manganese oxide and iron oxide in the manganese slag dissolve out, and at the same time, the calcium, aluminum and other minerals in the manganese slag are removed, generating a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0091] (5) The coke powder with a particle size of 100 mesh obtained in step (3) was washed with deionized water and then activated with O2 plasma. The activation time was set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0092] (6) The manganese-iron salt solution with a manganese-iron mass ratio of 1:1 generated by immersion in 2 mol / L sulfuric acid in step (4) is washed with deionized water and then subjected to plasma activation using the method in step (5).

[0093] (7) Stir the plasma-activated coke powder obtained in step (5) and the plasma-activated manganese iron salt solution obtained in step (6) in a mass ratio of 4:1 in an 80°C water bath until they are evenly dispersed and free of lumps.

[0094] (8) The resulting uniformly dispersed coke and manganese iron salt mixture was dried in an oven at 90°C for 24 hours.

[0095] (9) Take out the dried product from step (8) and mix it with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer. Set the ball milling time to 2 h and the rotation speed to 300 r / min. Stop the experiment every 30 min. Expel the gas in the ball mill tank to prevent the generated gas from causing excessive pressure in the tank.

[0096] (10) Place the product obtained in step (9) into a beaker, add 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate (mass ratio of 4:1), wash with deionized water, and then activate with O2 plasma. Set the activation time to 15 s, flow rate to 100 sccm, RF power to 100 W, and self-bias voltage to 300 V.

[0097] (11) Place the mixture of coke and manganese iron salt activated by mixed acid plasma in step (10) into an oven at 90°C and dry for 24 hours.

[0098] (12) Take out the dried mixture from step (11), put it in a quartz boat and place it in a tube furnace. Under N2 atmosphere, raise the temperature to 500°C at a heating rate of 7°C / min and pyrolyze for 2 hours, then cool to room temperature.

[0099] (13) The pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material. It is then dried in an oven at 90°C for 12 hours to obtain a new composite material of magnetic porous manganese slag and coke that is Fe-Mn modified by acid activation and is conducive to the adsorption of berberine hydrochloride.

[0100] Example 5

[0101] A method for preparing a magnetic porous electrolytic manganese slag and coke composite material for adsorbing berberine hydrochloride includes the following steps:

[0102] (1) Place 10g of electrolytic manganese slag (mainly composed of manganese oxide and iron oxide) in a 90℃ oven and dry for 30min. Place the dried manganese slag in a ball mill with a ball gradation of 6:4:1, a ball to manganese slag ratio of 5:1, and a rotation speed of 300r / min and ball mill for 1h to obtain manganese slag powder.

[0103] (2) The coke was crushed using a graded crusher and sieved using a standard sieve. Coke with a particle size of 100 mesh was selected as a sample.

[0104] (3) Place the coke in a 90℃ oven and dry for 30 minutes. After drying, pack it into bags for later use.

[0105] (4) The manganese slag powder obtained in step (1) is soaked in 100 mL of 3 mol / L sulfuric acid solution at 60 °C with a solid-liquid ratio of 1:15 g / L for 1.0 h. The manganese oxide and iron oxide in the manganese slag dissolve out, and at the same time, the calcium, aluminum and other minerals in the manganese slag are removed, generating a manganese-iron salt solution with a manganese-iron mass ratio of 1:1.

[0106] (5) The coke powder with a particle size of 100 mesh obtained in step (3) was washed with deionized water and then activated with O2 plasma. The activation time was set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

[0107] (6) The manganese-iron salt solution with a manganese-iron mass ratio of 1:1 generated by immersion in 3 mol / L sulfuric acid in step (4) is washed with deionized water and then subjected to plasma activation using the method in step (5).

[0108] (7) Stir the plasma-activated coke powder obtained in step (5) and the plasma-activated manganese iron salt solution obtained in step (6) in a water bath at 80°C at a mass ratio of 5:1 until they are evenly dispersed and free of lumps.

[0109] (8) The uniformly dispersed coke and manganese iron salt mixture obtained in step (7) is dried in an oven at 90°C for 24 hours.

[0110] (9) Take out the dried product from step (8) and mix it with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer. Set the ball milling time to 2 h and the rotation speed to 300 r / min. Stop the experiment every 30 min. Expel the gas in the ball mill tank to prevent the generated gas from causing excessive pressure in the tank.

[0111] (10) Place the product obtained in step (9) into a beaker, add 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate (mass ratio of 5:1), wash with deionized water, and then activate with O2 plasma. Set the activation time to 15 s, flow rate to 100 sccm, RF power to 100 W, and self-bias voltage to 300 V.

[0112] (11) Place the mixture of coke and manganese iron salt activated by mixed acid plasma in step (10) into an oven at 90°C and dry for 24 hours.

[0113] (12) Take out the dried mixture from the step, put it in a quartz boat and place it in a tube furnace. Under N2 atmosphere, raise the temperature to 500°C at a heating rate of 7°C / min and pyrolyze for 2 hours, then cool to room temperature.

[0114] (13) The pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material. It is then dried in an oven at 90°C for 12 hours to obtain a new composite material of magnetic porous manganese slag and coke that is Fe-Mn modified by acid activation and is conducive to the adsorption of berberine hydrochloride.

[0115] Experimental results

[0116] After comparing the adsorption properties of the aerogel materials prepared in Examples 1-5, it was found that the composite material prepared under the experimental conditions in Example 3 (see physical image) showed the best adsorption performance. Figure 2 The adsorption effect of ) is the best. Its SEM image is as follows. Figure 3 and Figure 4 As shown in the figure, it is clear that the composite material contains a porous structure and is loaded with iron-manganese oxides, which creates favorable conditions for the adsorption of berberine hydrochloride. The composite material prepared in Example 3 achieved a removal rate of over 90% for berberine hydrochloride. Figure 1 As can be seen, the composite material exhibits excellent adsorption capacity for berberine hydrochloride under different influencing factors. Furthermore, the prepared composite material also demonstrates good adsorption capacity in complex water bodies where different ions are present, such as... Figure 5As shown in the figure. Furthermore, the kinetics, isotherms, and thermodynamics of the prepared composite material for berberine hydrochloride revealed that the adsorption of berberine hydrochloride by this material is an endothermic monolayer chemisorption. Finally, the recycling performance of the prepared composite material was studied, and it was found that the material still exhibits good adsorption performance for berberine hydrochloride after five cycles.

[0117] It is understood that the above specific description of the present invention is only for illustrating the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effect; as long as the use needs are met, they are all within the protection scope of the present invention.

Claims

1. A method for preparing a composite material of berberine hydrochloride electrolytic manganese slag and coke, characterized in that, Follow these steps: (1) The dried electrolytic manganese slag is placed in a ball mill and ball-milled to obtain manganese slag powder; (2) The coke is crushed using a grading crusher and screened using a standard sieve with a particle size range of 20 to 100 mesh to obtain coke; (3) Place the coke obtained in step (2) into an oven and dry it; (4) Soak the manganese slag powder obtained in step (1) in sulfuric acid to generate a manganese iron salt solution; (5) The coke obtained in step (3) is washed with deionized water and then activated with O2 plasma; (6) The manganese iron salt solution obtained in step (4) is washed with deionized water and then activated with O2 plasma; (7) Stir the plasma-activated coke product obtained in step (5) and the plasma-activated manganese iron salt solution product obtained in step (6) in a water bath. (8) Place the product obtained in step (7) into an oven and dry it; (9) The product obtained in step (8) is mixed with acetic acid in a wet ball mill mixer; (10) The product obtained in step (9) is added to a mixed solution of trisodium citrate and oxalic acid dihydrate, washed with deionized water, and then activated with O2 plasma. (11) Place the product obtained in step (10) into an oven and dry it; (12) Place the product obtained in step (11) into a quartz boat and place it in a tube furnace. Under N2 atmosphere, heat the product by program and pyrolyze it, and then cool it to room temperature. (13) Wash the product obtained in step (12) with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the surface of the material, and dry it in an oven to obtain the target product.

2. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 1, characterized in that: In step (1), the electrolytic manganese slag is placed in a 90℃ oven and dried for 30 minutes; the dried electrolytic manganese slag is then placed in a ball mill with a ball gradation of 6:4:1, a ball-to-electrolytic manganese slag ratio of 3:1, and a rotation speed of 300 r / min and ball-milled for 1 hour to obtain manganese slag powder.

3. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 2, characterized in that: In step (4), the manganese slag powder obtained in step (1) is soaked in a solution with a sulfuric acid concentration of 0.5-2.0 mol / L, a temperature of 60℃, and a solid-liquid ratio of 1:15 g / L for 1.0 h to generate a manganese-iron salt solution with a manganese-iron mass ratio of 1:

1.

4. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 3, characterized in that: In step (5), the coke obtained in step (3) is washed with deionized water and then activated with O2 plasma; the activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

5. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 4, characterized in that: In step (6), the manganese iron salt solution obtained in step (4) is washed with deionized water and then activated with O2 plasma; the activation time is set to 15s, the flow rate to 100sccm, the radio frequency power to 100W, and the self-bias voltage to 300V.

6. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 5, characterized in that: In step (7), the plasma-activated coke product obtained in step (5) and the plasma-activated manganese iron salt solution product obtained in step (6) are stirred in an 80°C water bath at a mass ratio of 3 to 1:

1.

7. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 6, characterized in that: In step (9), the dried product from step (8) is taken out and mixed with 100 mL of 2 mol / L acetic acid in a wet ball mill mixer; the ball milling time is set to 2 h and the rotation speed is 300 r / min. The experiment is stopped every 30 min to remove the gas in the ball mill tank.

8. The method for preparing the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 7, characterized in that: In step (10), the product obtained in step (9) is added to 100 ml of a mixed solution of 1.0 mol / L trisodium citrate and oxalic acid dihydrate. After washing with deionized water, it is activated by O2 plasma with an activation time of 15 s, a flow rate of 100 sccm, a radio frequency power of 100 W, and a self-bias voltage of 300 V.

9. The preparation method of the composite material of berberine hydrochloride electrolytic manganese slag and coke according to claim 8, characterized in that: In step (12), the product obtained in step (11) is placed in a quartz boat and placed in a tube furnace. Under N2 atmosphere, the temperature is raised to 500°C at a heating rate of 7°C / min and pyrolyzed for 2 hours, and then cooled to room temperature.

10. The method for preparing the composite material of berberine hydrochloride electrolytic manganese slag and coke according to any one of claims 1 to 9, characterized in that: In step (13), the pyrolysis product obtained in step (12) is repeatedly washed with deionized water to remove free ions and residual trisodium citrate and oxalic acid dihydrate from the material surface, and then dried in an oven at 80°C for 12 hours to obtain the target product.

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