Preparation process of sophora flavescens lotion decoction dreg-based modified adsorption material

Abstract

The invention discloses a preparation process of a sophora flavescens lotion decoction dreg-based modified adsorption material, which comprises the following steps: (1) soaking sophora flavescens lotion decoction dregs in deionized water and ethanol in sequence for pretreatment to obtain pretreated decoction dreg powder; (2) sequentially carrying out composite chemical modification through a sodium bicarbonate solution and an acetic acid solution to obtain composite modified medicine residue powder; and (3) mixing with diatomite, granulating, and carrying out physical activation under a low-temperature microwave condition to prepare the adsorbing material. High-value utilization of the traditional Chinese medicine residues is achieved, the process is mild, energy consumption is low, a developed pore structure is formed while active ingredients of sophocarpidine in the medicine residues are reserved through synergistic modification, the obtained material has excellent adsorption performance and antibacterial function, the adsorption effect on heavy metal ions and phenolic organic matter is good, the mechanical strength is high, and the service life of the material is prolonged. The material can be widely applied to the field of sewage treatment.

Description

Technical Field

[0001] This invention relates to the field of waste treatment and functional materials in traditional Chinese medicine, specifically to a preparation process of a modified adsorbent material based on Sophora flavescens decoction residue. Background Technology

[0002] With the rapid development of the pharmaceutical industry, the large amount of medicinal residue generated during the production of traditional Chinese medicine has become an unavoidable solid waste. Traditional treatment methods such as landfill and incineration not only waste resources but may also cause environmental pollution. Kushen (Sophora flavescens) washings, as a commonly used traditional Chinese medicine preparation, still contain certain amounts of matrine, oxymatrine, cellulose, lignin, and flavonoids in their residue, possessing potential for further resource utilization.

[0003] Current research has explored the use of plant-based waste in the preparation of adsorbent materials, but most methods employ strong acid / base modification or high-temperature carbonization, resulting in high energy consumption, severe damage to active groups, and poor material stability. Furthermore, traditional modification methods often overlook the synergistic adsorption and antibacterial effects of residual active components in the waste residue, leading to materials with limited functionality and applicability.

[0004] Therefore, developing a green, efficient, and low-energy-consumption process for preparing adsorbent materials based on medicinal residues, and making full use of the inherent active components in the residues to achieve targeted regulation of their structure and adsorption performance, has significant environmental value and application prospects. Summary of the Invention

[0005] To realize the resource utilization of Sophora flavescens washing residue, this invention provides a preparation process for Sophora flavescens washing residue-based modified adsorbent material.

[0006] The first technical solution adopted in this invention is as follows: A preparation process of a modified adsorbent material based on Sophora flavescens washing residue includes the following steps: ① Pretreatment: Sophora flavescens washing residue is soaked in deionized water and ethanol in sequence to remove impurities, then dried, pulverized, and sieved to obtain pretreated residue powder; ② Composite chemical modification: The pretreated residue powder is treated in sequence with sodium bicarbonate solution and acetic acid solution, washed until neutral, then dried and pulverized to obtain composite modified residue powder; ③ Low-temperature physical activation: The composite modified residue powder is mixed with diatomaceous earth, granulated with water, and activated under low-temperature microwave conditions to obtain the adsorbent material.

[0007] Preferably, in step ①: the liquid-to-solid ratio for soaking in deionized water is (10-14):1, the soaking is at room temperature, and the soaking time is 3-5 hours; the liquid-to-solid ratio for soaking in ethanol is (8-12):1, the soaking temperature is 30-40℃, and the soaking time is 1.5-2.5 hours; the drying temperature is 70-90℃, and the drying time is 7-9 hours; the sieve mesh size is 100-120 mesh.

[0008] Preferably, in step ②: the concentration of sodium bicarbonate solution is 1.5-3 mol / L, the liquid-to-solid ratio is (14-18):1, the reaction temperature is 50-60℃, and the reaction time is 2.5-3.5 h; the concentration of acetic acid solution is 0.8-1.8 mol / L, the liquid-to-solid ratio is (12-16):1, the reaction temperature is 40-50℃, and the reaction time is 1-1.5 h.

[0009] Preferably, in step ③: the mass ratio of diatomaceous earth to composite modified drug residue powder is 1:(5-7); the particle diameter after granulation is 2-4mm; the microwave treatment power is 300-600W, the temperature is 110-140℃, and the time is 25-35min.

[0010] The second technical solution adopted in this invention is as follows: a modified adsorbent material based on Sophora flavescens decoction residue, having the following performance indicators: specific surface area of ​​90-130 m² / g. 2 / g; for Cu 2+ Zn 2+ The adsorption capacity is ≥55mg / g; the adsorption rate for phenolic organic pollutants is ≥90%; the particle mechanical strength is ≥92%; the inhibition rate against Escherichia coli is ≥30%; and the number of adsorption-desorption cycles is ≥6 times.

[0011] The third technical solution adopted in this invention is as follows: the application of a modified adsorbent material based on Sophora flavescens decoction residue in sewage treatment, used to adsorb heavy metal ions and / or organic pollutants in water.

[0012] Preferably, the heavy metal ions include Cu. 2+ With Zn 2+ Organic pollutants include phenolic compounds.

[0013] The present invention has the following beneficial effects: 1. Resource utilization of Sophora flavescens washing residue: Using Sophora flavescens washing residue produced by pharmaceutical companies as raw material, this process transforms it into high-performance adsorption material, effectively solving the problem of solid waste treatment of traditional Chinese medicine, turning waste into treasure, and conforming to the concept of green and circular sustainable development. 2. Mild preparation process: The "sodium bicarbonate-acetic acid" composite chemical modification system used is a mild modification, avoiding the damage of active groups such as hydroxyl and amino groups in the medicinal residue by strong acids and alkalis, and preserving its natural adsorption structure; "low-temperature microwave physical activation" is used instead of high-temperature carbonization process, which has lower energy consumption and is conducive to preserving the biomass active components in the medicinal residue; the material structure is stable, the number of adsorption and desorption cycles is ≥6 times, the regeneration performance is good, and the use cost is reduced; 3. High adsorption performance: Through composite chemical modification and synergistic granulation and activation with diatomaceous earth, the material forms a well-developed microporous-mesoporous structure with a specific surface area of ​​90-130 m². 2 / g, for Cu 2+ Zn 2+ The adsorption capacity is ≥55mg / g, and the adsorption rate for phenolic organic pollutants is ≥90%. 4. Antibacterial properties: The "water-ethanol stepwise pretreatment" effectively removes impurities while selectively retaining the inherent active ingredients such as matrine in the residue, so that the final material has weak antibacterial properties on the basis of physicochemical adsorption of pollutants. 5. High mechanical strength: The granular material produced by compounding diatomaceous earth and microwave activation granulation has a mechanical strength of ≥92%, has good physical stability, and is easy to fill and handle in practical applications; 6. Significant wastewater treatment effect: It is particularly suitable for wastewater treatment and can efficiently and simultaneously remove a variety of heavy metal ions and organic pollutants from water bodies, showing good market application prospects. Detailed Implementation

[0014] The present invention will be further described below with reference to the embodiments.

[0015] Raw materials and equipment used in each embodiment Sophora flavescens wash residue: provided by Zhejiang Zhongfa Pharmaceutical Co., Ltd., the main components are matrine and oxymatrine residue, containing cellulose, lignin and flavonoids, initial particle size ≤8mm, moisture content ≤20%; Diatomaceous earth: purchased from the market, particle size 800 mesh, purity ≥96%.

[0016] Reagents: Deionized water, medical-grade ethanol (95% purity), sodium bicarbonate, and acetic acid, all of analytical grade.

[0017] Equipment: forced-air drying oven, constant temperature water bath, high-speed mixer, low-temperature microwave equipment.

[0018] Example 1 Step 1: Targeted pretreatment of Sophora flavescens washing residue.

[0019] Weigh 100g of waste residue from Sophora flavescens washings and place it in a reactor. Add 1200mL of deionized water at a liquid-to-solid ratio of 12:1. Stir and soak at 180r / min for 4 hours at room temperature to wash away residual washing components on the surface.

[0020] After filtration, add 1000 mL of medical-grade ethanol to the filter cake at a liquid-to-solid ratio of 10:1, and soak it in a constant temperature water bath at 35°C for 2 hours to remove fat-soluble impurities and pigments.

[0021] The filter cake was filtered again and placed in a forced-air drying oven to dry at 80°C for 8 hours.

[0022] The dried medicinal residue is crushed using a pulverizer and passed through a 100-mesh sieve to obtain pretreated Sophora flavescens medicinal residue powder. It is then sealed and stored away from light to prevent the oxidation of the alkaloid components.

[0023] Step 2: Composite chemical modification.

[0024] Weigh 50g of pretreated Sophora flavescens residue powder and add it to 800mL of 2mol / L sodium bicarbonate solution at a liquid-to-solid ratio of 16:1. Stir the mixture at 280r / min for 3 hours in a constant temperature water bath at 55℃.

[0025] After the reaction was completed, the filter was repeatedly rinsed with deionized water until the pH of the filtrate was 7, thus obtaining the alkali-modified Sophora flavescens residue filter cake.

[0026] The filter cake was added to 700 mL of 1.2 mol / L acetic acid solution at a liquid-to-solid ratio of 14:1. The mixture was stirred and reacted for 1.2 hours in a constant temperature water bath at 45°C.

[0027] After filtration, the solid product was dried at 75°C for 6 hours, pulverized, and passed through a 120-mesh sieve to obtain composite modified Sophora flavescens residue powder.

[0028] Step 3: Low-temperature physical activation.

[0029] Weigh 60g of compound modified Sophora flavescens residue powder, add 10g of diatomaceous earth at a mass ratio of 6:1, and mix evenly.

[0030] Add an appropriate amount of deionized water to the mixture to adjust the moisture content to about 40%, and then stir it for 18 minutes at a speed of 550 r / min with a high-speed mixer to make it evenly mixed and have good plasticity.

[0031] The mixture is granulated into cylindrical particles with a diameter of about 3 mm using a granulator.

[0032] The particles were evenly spread in a low-temperature microwave device, the microwave power was set to 450W, the temperature was controlled at 125℃, and the treatment lasted for 30 minutes.

[0033] After processing, the material is allowed to cool naturally to room temperature. Particles with intact shapes and no cracks are then screened out to obtain the finished product of the modified adsorbent material based on Sophora flavescens decoction residue, which is denoted as sample S1.

[0034] Example 2 The main difference between this embodiment and Embodiment 1 lies in the adjustment of process parameters.

[0035] Pretreatment in step one: the solid-liquid ratio of deionized water is 11:1, and the time is 3.5 hours; the solid-liquid ratio of ethanol is 9:1, the temperature is 38℃, and the time is 1.8 hours; the drying temperature is 85℃, and the time is 7.5 hours; the sieve mesh is 110 mesh.

[0036] In step two, the chemical modification was carried out as follows: the concentration of sodium bicarbonate solution was 1.8 mol / L, the liquid-to-solid ratio was 15:1, the reaction temperature was 58℃, and the reaction time was 2.8 hours; the concentration of acetic acid solution was 1.0 mol / L, the liquid-to-solid ratio was 13:1, the reaction temperature was 48℃, and the reaction time was 1 hour.

[0037] In step three, physical activation is performed as follows: the mass ratio of drug residue powder to diatomaceous earth is 5.5:1; the granulation diameter is 2.5 mm; the microwave power is 380 W, the temperature is 115 ℃, and the time is 35 minutes.

[0038] The resulting modified adsorbent material based on Sophora flavescens washing residue is designated as sample S2.

[0039] Example 3 This embodiment is an implementation of Embodiment 1 using a different set of process parameters.

[0040] Pretreatment in step one: the solid-liquid ratio of deionized water is 13:1, and the time is 4.5 hours; the solid-liquid ratio of ethanol is 11:1, the temperature is 32℃, and the time is 2.2 hours; the drying temperature is 75℃, and the time is 8.5 hours; the sieve mesh is 115 mesh.

[0041] In step two, the chemical modification was carried out as follows: the concentration of sodium bicarbonate solution was 2.5 mol / L, the liquid-to-solid ratio was 17:1, the reaction temperature was 52℃, and the reaction time was 3.2 hours; the concentration of acetic acid solution was 1.6 mol / L, the liquid-to-solid ratio was 15:1, the reaction temperature was 42℃, and the reaction time was 1.4 hours.

[0042] In step three, physical activation was performed using a 6.5:1 mass ratio of drug residue powder to diatomaceous earth; a granulation diameter of 3.5 mm; a microwave power of 500 W; a temperature of 135 °C; and a time of 32 minutes.

[0043] The resulting modified adsorbent material based on Sophora flavescens washing residue is designated as sample S3.

[0044] Comparative Example The comparative example used the same pretreated drug residue powder as in Example 1, but without the composite chemical modification in step two, and without the addition of diatomaceous earth and microwave activation. That is, the pretreated drug residue powder was directly granulated and dried, and the resulting material was recorded as sample D.

[0045] Effect verification experiment The performance of samples S1, S2, S3 obtained in Examples 1-3 and comparative sample D were tested, and the results are shown in the table below.

[0046] The testing methods for each performance indicator are as follows: Specific surface area was determined using nitrogen adsorption-desorption method; The adsorption capacity of heavy metal ions and the adsorption rate of phenolic organic pollutants were both determined using static adsorption experiments. The mechanical strength of the particles was determined by the drop strength test. The antibacterial rate was determined using Escherichia coli as the test strain and a quantitative suspension test was conducted. Adsorption-desorption cycle stability was determined by multiple adsorption-desorption cycle experiments, requiring a capacity retention rate of ≥85% after desorption.

[0047]

[0048] As shown in the table above, the adsorbent materials (S1-S3) prepared using the process of this invention are significantly superior to the unmodified and physically activated comparative materials (D) in terms of specific surface area, adsorption capacity for heavy metals and organic pollutants, mechanical strength, antibacterial properties, and cycle stability. This indicates that this invention, through the synergistic effect of "composite chemical modification" and "low-temperature physical activation," successfully transforms the residue of Sophora flavescens extract into a high-performance, multifunctional adsorbent material, fully achieving the expected technical effects.

[0049] Obviously, the above embodiments of the present invention are merely illustrative examples to illustrate the invention and are not intended to limit the implementation of the invention. Other obvious variations or modifications derived from the essential spirit of the invention still fall within the protection scope of the invention.

Claims

1. A preparation process of a Sophora flavescens lotion residue-based modified adsorption material, characterized in that, The method comprises the following steps: ① Pretreatment: the residue of Sophora flavescens lotion is sequentially soaked in deionized water and ethanol, impurities are removed, and then the residue is dried, crushed, and sieved to obtain pretreated residue powder; ② Compound chemical modification: the pretreated residue powder is sequentially treated with sodium bicarbonate solution and acetic acid solution, washed until neutral, dried, and crushed to obtain compound modified residue powder; ③ Low-temperature physical activation: the compound modified residue powder is mixed with diatomite, granulated after adding water, and then activated under low-temperature microwave conditions to obtain an adsorption material.

2. The preparation process of the Sophora flavescens lotion residue-based modified adsorption material according to claim 1, characterized in that, In step ①: The liquid-solid ratio of deionized water soaking is (10-14):1, the soaking is carried out at room temperature, and the soaking time is 3-5 h; The liquid-solid ratio of ethanol soaking is (8-12):1, the soaking temperature is 30-40℃, and the soaking time is 1.5-2.5 h; The drying temperature is 70-90℃, and the time is 7-9 h; The sieving mesh number is 100-120 mesh.

3. The process for preparing the modified adsorbing material of Sophora flavescens residue base according to claim 1, characterized in that, In step ②: The concentration of sodium bicarbonate solution is 1.5-3 mol / L, the liquid-solid ratio is (14-18):1, the reaction temperature is 50-60℃, and the reaction time is 2.5-3.5 h; The concentration of acetic acid solution is 0.8-1.8 mol / L, the liquid-solid ratio is (12-16):1, the reaction temperature is 40-50℃, and the reaction time is 1-1.5 h.

4. The process for preparing the Sophora flavescens lotion residue-based modified adsorption material according to claim 1, characterized in that, In step ③: The mass ratio of diatomite to compound modified residue powder is 1:(5-7); The particle diameter after granulation is 2-4 mm; The microwave treatment power is 300-600 W, the temperature is 110-140℃, and the time is 25-35 min.

5. The adsorptive material prepared according to the preparation process of the residue of Sophora flavescens lotion modified adsorptive material according to any one of claims 1-4, characterized in that, The adsorption rate of phenolic organic pollutants is ≥90%; The specific surface area is 90-130 m 2 / g; Adsorption capacity for Cu 2+ , Zn 2+ ≥ 55 mg / g; The particle mechanical strength is ≥92%; The antibacterial rate of Escherichia coli is ≥30%, and the adsorption-desorption cycle use frequency is ≥6 times. The method is used for adsorbing heavy metal ions and / or organic pollutants in water bodies.

6. Use of the adsorbent material according to claim 5 in sewage treatment, characterized in that, ​ 7. Use according to claim 6, characterized in that, Heavy metal ions include Cu 2+ With Zn 2+ Organic pollutants include phenolic compounds.

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