Scutellaria baicalensis processing plant waste comprehensive treatment method and system

Abstract

The invention relates to a comprehensive treatment method and system for waste of a scutellaria baicalensis processing plant. The waste comprises acidic waste liquid generated by scutellaria baicalensis water extraction and precipitation and biogas slurry generated by anaerobic fermentation of scutellaria baicalensis extraction dregs. According to the method, biogas slurry generated after anaerobic fermentation of medicine residues generated by extracting baicalin in a scutellaria baicalensis processing plant is mixed with biomass ash residues to obtain a mixed solution, ammonia nitrogen in the mixed solution is efficiently removed by adopting an ammonia stripping technology, and acidic waste liquid generated in an astragaloside extraction process is used as absorption liquid to treat stripping ammonia gas; the mixed solution after ammonia stripping absorbs H2S in the biogas, so that the element S is enriched in the mixed solution, the comprehensive resource utilization of the biogas slurry, the biomass ash, the acid filtrate and the biogas is achieved, meanwhile, a stock solution containing nutrient substances such as P, K, S and NH4 < + >-N is produced and used for further producing and processing organic liquid fertilizer subsequently, and the purposes of treating waste with waste and recycling resources of scutellaria baicalensis processing factories are achieved.

Description

Technical Field

[0001] The present invention relates to the field of environmental protection, and particularly to a comprehensive treatment method and system for waste from a Scutellaria baicalensis processing factory. Background Art

[0002] Baicalin is a flavonoid compound extracted and isolated from the dried roots of the traditional Chinese medicine Scutellaria baicalensis. It has significant biological activities, including antibacterial, diuretic, anti-inflammatory, cholesterol-lowering, anti-thrombotic, asthma-relieving, fire-purging and detoxifying, hemostatic, fetal-protecting, anti-allergic reaction and spasmolytic effects. It is also a specific inhibitor of mammalian liver sialidase, has the effect of regulating certain diseases, and also has a strong anti-cancer reaction physiological efficacy.

[0003] Scutellaria baicalensis processing factories usually adopt the water extraction and acid precipitation method to extract baicalin, including the following steps: Step (1) is to perform water extraction on Scutellaria baicalensis and filter to obtain a water extraction filtrate and medicinal residues; Step (2) is to adjust the pH value of the water extraction filtrate to acidic, separate, and discard the supernatant, and the precipitate is baicalin. Two major wastes need to be post-treated during this process. One is the medicinal residues in Step (1), which are generally anaerobically fermented to obtain biogas slurry and biogas. The biogas slurry is recycled to farmland, and the biogas is used for combustion. However, the biogas slurry contains a high concentration of ammonia, and directly recycling it to farmland is likely to cause plant growth disorders; the biogas contains a large amount of H 2 S, which needs to be further removed to avoid pipeline corrosion; the other is the supernatant in Step (2). Due to its strong acidity (pH < 2), it cannot be directly discharged, and most of it can only be treated by methods such as neutralization treatment and chemical precipitation, resulting in an increase in treatment costs. Therefore, it is necessary to study a more efficient, more economical and more environmentally friendly integrated comprehensive treatment method and device for the waste from Scutellaria baicalensis processing factories.

[0004] Biomass ash residue is the ash residue generated by biomass power plants burning biomass fuels such as straw and wood. It is the main waste generated during the power generation process of biomass power plants in China at present. Currently, biomass ash residues are directly discarded or used for paving roads and making bricks, with low utilization rate and low economic added value. In some areas, the treatment of biomass incineration ash residues also requires enterprises to bear certain disposal costs, increasing the operation costs of power plants and reducing economic benefits. There have been research reports on modifying biomass ash residues to prepare fillers for wastewater treatment, but the modification effect is not good and the wastewater treatment efficiency is low. Summary of the Invention

[0005] The purpose of the present invention is to provide a comprehensive treatment system for waste from a Scutellaria baicalensis processing factory, including a reaction tower (1), a feeding device (2), a tail gas absorption tower (3) and an enrichment tower (33);

[0006] The top of the reaction tower (1) is fixedly connected with a feed pipeline (8) and an exhaust pipeline (15). The feed pipeline (8) is connected to a feeding device (2), and a feed pump (28), a feed solenoid valve (7), and an exhaust check valve (17) are fixedly installed. The first exhaust pipeline (15) is connected to a tail gas absorption tower (3), and a first exhaust solenoid valve (16) is fixedly installed.

[0007] The bottom of the reaction tower (1) is fixedly connected with an intake pipeline (13). An intake solenoid valve (12) is fixedly installed on the intake pipeline (13), and the intake pipeline (13) is externally connected to a blower (11).

[0008] The bottom side of the reaction tower (1) is fixedly connected with a drain pipeline (27). A drain solenoid valve (26) is fixedly installed on the drain pipeline (27). The drain pipeline (27) is connected to a reflux valve (32) and an enrichment tower (33), and the reflux valve (32) is installed on a reflux pipeline (31).

[0009] In a preferred technical solution of the present invention, a water distributor (101) is fixedly installed at the top inside the reaction tower (1). A first mesh partition (104) is fixedly installed in the upper part inside the reaction tower (1), and a second mesh partition (102) is fixedly installed in the lower part. A first packing layer (103) is placed in the space between the first mesh partition and the second mesh partition. A pressure relief pipeline (29) is fixedly installed at the top outside the reaction tower (1), and a pressure relief valve (30) is fixedly installed on the pressure relief pipeline (29).

[0010] In a preferred technical solution of the present invention, a liquid level gauge (14) is fixedly installed at the top inside the reaction tower (1).

[0011] In a preferred technical solution of the present invention, a touch all-in-one machine (25) is installed on one side of the reaction tower (1). The touch all-in-one machine (25) is respectively connected to a feed solenoid valve (7), a blower (11), an intake solenoid valve (12), a liquid level gauge (14), an exhaust solenoid valve (16), an exhaust solenoid valve (18), a gas monitor (19), an acid liquid circulation pump (20), a pH monitor (21), a drain solenoid valve (26), a feed pump (28), a pressure relief valve (30), a reflux valve (32), a biogas exhaust solenoid valve (36), and a biogas slurry circulation pump (38).

[0012] In a preferred technical solution of the present invention, a water inlet pipeline (10) is fixedly installed on one side of the feeding device (2). A spiral stirrer (5) is installed inside the feeding device (2), and a material bin (6) is fixedly installed at the top. The material bin (6) is equipped with a motor (9) to control the spiral stirrer (5) inside the material bin. A control panel (4) is fixedly installed at the top of the feeding device (2), and the control panel (4) is respectively connected to the motor (9) and the spiral stirrer (5).

[0013] In a preferred technical solution of the present invention, an acid solution circulation water tank (301) is arranged at the bottom inside the tail gas absorption tower (3). A pH monitor (21) is fixedly installed on the acid solution circulation water tank (301). The acid solution circulation water tank (301) is externally connected to an acid solution circulation pipeline (23). An acid solution circulation pump (20) is fixedly installed on the acid solution circulation pipeline (23). The acid solution circulation pump (20) is connected to a spraying area through an acid solution spraying pipeline (22). An acid solution spraying head (303) is fixedly installed at the bottom of the spraying pipeline (22) inside the tail gas absorption tower (3). A second packing layer (302) is fixedly installed inside the tail gas absorption tower (3). A cyclone demister (304) is fixedly installed at the top inside the tail gas absorption tower (3).

[0014] In a preferred technical solution of the present invention, a second exhaust gas pipeline (24) is fixedly installed at the top outside the tail gas absorption tower (3). A gas monitor (19) and a second exhaust gas solenoid valve (18) are fixedly installed on the second exhaust gas pipeline (24).

[0015] In a preferred technical solution of the present invention, a biogas slurry circulation water tank (331) is arranged at the bottom inside the enrichment tower (33). The biogas slurry circulation water tank (331) is externally connected to a biogas slurry circulation pipeline (37). A biogas slurry circulation pump (38) is fixedly installed on the biogas slurry circulation pipeline (37). The biogas slurry circulation pump (38) is connected to a spraying area through a biogas slurry spraying pipeline (37). A biogas slurry spraying head (332) is fixedly installed on the spraying pipeline inside the enrichment tower (33). A third packing layer (333) is fixedly installed inside the enrichment tower (33).

[0016] In a preferred technical solution of the present invention, a biogas inlet pipeline (34) is fixedly installed at the bottom outside the enrichment tower (33), and a biogas exhaust pipeline (35) is fixedly installed at the top. A biogas exhaust solenoid valve (36) is fixedly installed on the biogas exhaust pipeline (35). A liquid discharge pipeline (39) is fixedly installed at the bottom of the enrichment tower (33). A liquid discharge solenoid valve (40) is fixedly installed on the liquid discharge pipeline (39).

[0017] Another object of the present invention is to propose a comprehensive treatment method for the waste of a Scutellaria baicalensis processing factory. The waste includes acidic waste liquid generated by water extraction and precipitation of Scutellaria baicalensis and biogas slurry generated by anaerobic fermentation of Scutellaria baicalensis extraction residue. The treatment of the waste specifically includes the following steps:

[0018] (1) Feed the biogas slurry to be processed into the feeding device (2) through the water inlet pipeline (10). At the same time, start the spiral stirrer (5) fixedly installed in the feeding device (2) and start the motor (9) fixedly installed at the top of the feeding device (2). Control the rotation of the screw in the material bin, and the biomass ash in the material bin (6) drops into the feeding device (2) along with the rotating screw. Under the action of the spiral stirrer (5), the biogas slurry and the biomass ash are fully mixed to obtain a mixed liquid;

[0019] (2) Open the feed pump (28) and the feed solenoid valve (7), and close the intake solenoid valve (12), the exhaust solenoid valve (16) and the drain solenoid valve (26). The mixed liquid in step (1) flows into the reaction tower (1) through the feed pipeline (8) and the exhaust check valve (17), and flows through the first packing layer (103). When the feed liquid level rises to the stop liquid level set by the liquid level gauge (14), open the intake solenoid valve (12), the blower (11), and the exhaust solenoid valve (16) to start aeration for ammonia stripping. The aeration intensity is 180 m 3 / (m 2 ·h), and the stripping time is 30 - 40 min; Open the drain solenoid valve (26) and the pressure relief valve (30), and close the intake solenoid valve (12) and the exhaust solenoid valve (16). The biogas slurry after aeration treatment is discharged through the drain pipeline (27) and flows into the enrichment tower (33); The tail gas after aeration treatment enters the tail gas absorption tower (3) through the exhaust pipeline (15);

[0020] (3) Fill the acidic waste liquid to be processed into the acid liquid circulation water tank (301) arranged at the bottom inside the tail gas absorption tower (3). Start the exhaust solenoid valve (18) and the acid liquid circulation pump (20). The acidic waste liquid passes through the acid liquid circulation pipeline (23), the acid liquid circulation pump (20) and the spray pipeline

[0021] (22) is sprayed out by the spray head (303), and contacts with the tail gas entering the tail gas absorption tower (3) through the exhaust pipeline (15) in step (2) on the surface of the second packing layer (302). The treatment liquid flows into the lower acid liquid circulation water tank for reuse. When the pH monitor (21) fixedly installed on one side of the acid liquid circulation water tank (301) shows that the pH of the treatment liquid > 6, discharge the treatment liquid 1; The remaining tail gas rises to the cyclone demister (304) and is discharged after being monitored by the gas monitor (19);

[0022] (4) Feed the biogas slurry after aeration treatment in step (2) into the enrichment tower (33). The biogas generated by the anaerobic fermentation system enters the enrichment tower through the biogas inlet pipeline (34). At the same time, open the biogas exhaust solenoid valve (36), the biogas slurry circulation pump (38) and the drain solenoid valve (40). The biogas slurry is sprayed into the enrichment tower through the biogas slurry spray head (332) to contact with the biogas, and absorb H in the biogas 2S is discharged through the liquid drainage pipeline (39) to obtain the treated liquid 2, which is used for subsequent further production and processing of organic liquid fertilizer. After the biogas passes through the third packing layer (333), the desulfurized biogas is discharged through the biogas exhaust pipeline and used for power generation.

[0023] In the preferred technical solution of the present invention, in step (1), the biogas slurry to be treated is the biogas slurry obtained after anaerobic fermentation of the medicinal residues collected from the Scutellaria baicalensis processing factory.

[0024] In the preferred technical solution of the present invention, in step (1), the biogas slurry to be treated has a COD of 5000 - 10000 mg / L, ammonia nitrogen of 1000 - 3000 mg / L, total nitrogen of 1000 - 3000 mg / L, total phosphorus of 100 - 500 mg / L, and a pH of 6 - 9.

[0025] In the preferred technical solution of the present invention, in step (1), the biomass ash residue is the residue after incineration of biomass waste.

[0026] In the preferred technical solution of the present invention, in step (1), the biomass ash residue is the residue after incinerating biomass waste at 800 - 1000 °C for 40 - 60 min.

[0027] In the preferred technical solution of the present invention, in step (1), the mass - volume ratio of the biomass ash residue to the biogas slurry to be treated is 20 - 30:1 (kg / L).

[0028] In the preferred technical solution of the present invention, in step (2), the aeration intensity is 100 - 200 m 3 / (m 2 ·h), and the stripping time is 30 - 40 min.

[0029] In the preferred technical solution of the present invention, in step (2), the biogas slurry after aeration treatment is discharged through the drainage pipeline (27), with part of it recycled to the aforementioned biogas slurry anaerobic fermentation process and part flowing into the enrichment tower (33).

[0030] In the preferred technical solution of the present invention, in step (2), 50 - 70% of the biogas slurry after aeration treatment is recycled to the hydrolysis acidification tank of the front - end anaerobic fermentation process.

[0031] In the preferred technical solution of the present invention, in step (2), the volume of the modified biomass filler in the first packing layer is 20 - 30% of the volume of the reaction tower (1).

[0032] In the preferred technical solution of the present invention, the fillers of the first packing layer (103), the second packing layer (302), and the third packing layer (333) are all modified biomass fillers.

[0033] In the preferred technical solution of the present invention, in step (4), the treatment liquid 2 can be used for subsequent further production and processing of organic liquid fertilizer.

[0034] In the preferred technical solution of the present invention, treatment liquid 1 and treatment liquid 2 are compounded in a volume ratio of 1:1-2 to prepare a water-soluble fertilizer, which can meet the water-soluble fertilizer standard of agricultural biogas slurry (GB / T 40750-2021) and be reused in farmland.

[0035] In the preferred technical solution of the present invention, in step (4), the H 2 S content in the desulfurized biogas meets the quality requirements of biogas for power generation in the Technical Code for Large and Medium-sized Biogas Projects (GB / T 51063-2014), and can be reused for power generation by biogas generators or combustion heating by biogas boilers.

[0036] In the preferred technical solution of the present invention, for the modified biomass filler, its preparation method includes the following steps:

[0037] (1) Add biomass ash residue to a ball mill, and gradually spray acetic acid solution with a concentration of 20-30% during the ball milling process. The mass ratio of the acetic acid solution to the biomass ash residue is 1:30-50. Granulate to form spherical particles with a diameter of 5-8 mm, dry them, and increase the temperature from room temperature to 400-500 °C at a heating rate of 10-15 °C / min, and keep them at 400-500 °C for heat preservation and roasting for 1-2 h to obtain biomass ash residue particles;

[0038] (2) Wash the biomass ash residue particles obtained in step (1) with water, soak them for 24-48 h and then dry them. Under nitrogen protection, increase the temperature from room temperature to 800-900 °C at a heating rate of 10-15 °C / min, and keep them at 800-900 °C for heat preservation and firing for 4-6 h;

[0039] (3) Immerse the biomass ash residue particles after firing in step (2) in a mixed solution of 20% HNO 3 and 20% H 2 SO 4 , perform ultrasonic treatment for 30-60 min, stir and heat under reflux for oxidation in a water bath at 70-80 °C for 3-4 h, cool and then repeatedly rinse with ultrapure water until the pH is neutral, and dry to constant weight;

[0040] (4) Place the biomass ash residue particles after drying in step (3) in an Fe 2 (NO) 3 solution according to a mass ratio of 1:10-20, oscillate at 100-150 rpm for 12-24 h, then let it stand for 24 h, increase the temperature from room temperature to 400-500 °C at a heating rate of 10-15 °C / min, and keep it at 400-500 °C for heat preservation and roasting for 3-4 h to obtain the product.

[0041] In the preferred technical solution of the present invention, in step (1), the ball milling conditions are that the rotational speed of the ball mill cylinder is 30 - 50 r / min.

[0042] In the preferred technical solution of the present invention, in step (1), the drying conditions are drying at 100 - 105 °C.

[0043] In the preferred technical solution of the present invention, in step (3), the 20% HNO 3 and 20% H 2 SO 4 The volume ratio is (1 - 2) : 1.

[0044] In the preferred technical solution of the present invention, in step (3), the ultrasonic conditions are 20 - 40 kHz, and the ultrasonic treatment is 30 - 60 min.

[0045] In the preferred technical solution of the present invention, in step (3), the drying conditions are drying at 100 - 105 °C.

[0046] The purpose of the present invention is to provide a modified biomass filler, and its preparation method includes the following steps:

[0047] (1) Add biomass ash residue to a ball mill, gradually spray acetic acid solution with a concentration of 20 - 30% during the ball milling process. The mass ratio of the acetic acid solution to the biomass ash residue is 1 : 30 - 50, granulate to form spherical particles with a diameter of 5 - 8 mm, dry, and increase the temperature from room temperature to 400 - 500 °C at a heating rate of 10 - 15 °C / min, and keep roasting at 400 - 500 °C for 1 - 2 h to obtain biomass ash residue particles;

[0048] (2) Wash the biomass ash residue particles obtained in step (1) with water, soak for 24 - 48 h and then dry, and increase the temperature from room temperature to 800 - 900 °C at a heating rate of 10 - 15 °C / min under nitrogen protection, and keep firing at 800 - 900 °C for 4 - 6 h;

[0049] (3) Immerse the biomass ash residue particles fired in step (2) in a mixed solution of 20% HNO 3 and 20% H 2 SO 4 , perform ultrasonic treatment for 30 - 60 min, stir and heat under reflux for oxidation in a water bath at 70 - 80 °C for 3 - 4 h, cool, and repeatedly rinse with ultrapure water until the pH is neutral, and dry to constant weight;

[0050] (4) Place the biomass ash residue particles dried in step (3) in Fe according to a mass ratio of 1 : 10 - 20 2 (NO) 3In the solution, after oscillating at 100 - 150 rpm for 12 - 24 h, then standing still for 24 h, heating from room temperature to 400 - 500 °C at a heating rate of 10 - 15 °C / min, and maintaining the temperature at 400 - 500 °C for heat baking for 3 - 4 h, it can be obtained.

[0051] In the preferred technical solution of the present invention, in step (1), the ball milling conditions are that the rotating speed of the ball mill cylinder is 30 - 50 r / min.

[0052] In the preferred technical solution of the present invention, in step (1), the drying conditions are drying at 100 - 105 °C.

[0053] In the preferred technical solution of the present invention, in step (3), the volume ratio of the 20% HNO 3 and 20% H 2 SO 4 is (1 - 2):1.

[0054] In the preferred technical solution of the present invention, in step (3), the ultrasonic conditions are 20 - 40 kHz, and the ultrasonic treatment is for 30 - 60 min.

[0055] In the preferred technical solution of the present invention, in step (3), the drying conditions are drying at 100 - 105 °C.

[0056] Another object of the present invention is to provide the application of the modified biomass filler of the present invention in water treatment.

[0057] Unless otherwise specified, when the present invention relates to the percentage between liquids, the percentage is volume / volume percentage; when the present invention relates to the percentage between a liquid and a solid, the percentage is volume / weight percentage; when the present invention relates to the percentage between a solid and a liquid, the percentage is weight / volume percentage; and the rest is weight / weight percentage.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] 1. The present invention uses biomass ash residue to prepare a modified biomass filler, which can effectively adsorb and intercept pollutants, reduce pollutants in wastewater such as SS, COD, nitrogen and phosphorus, improve the wastewater treatment efficiency, and at the same time can also remove sulfur in biogas, realizing the efficient treatment of biogas.

[0060] 2. The present invention mixes the biogas slurry generated by anaerobic fermentation of the medicinal residues produced by the Scutellaria baicalensis processing factory for extracting baicalin and biomass ash residue. The mixed solution uses the ammonia stripping technology to efficiently remove ammonia nitrogen, and uses the acidic waste liquid generated during the extraction process of astragaloside as the absorption liquid to treat the stripped ammonia. The mixed solution after stripping absorbs H in biogas 2Enrich the element S in S to achieve the comprehensive utilization of biogas slurry, biomass ash residue, acidic filtrate and biogas, and at the same time produce a stock solution containing nutrients such as P, K, S and NH4 + -N, etc., which is used for further production and processing of organic liquid fertilizer in the future, realizing waste treatment with waste and resource recycling of the Scutellaria baicalensis processing factory. Compared with the commercial liquid fertilizer, the cost can be reduced by about 110 yuan per ton.

[0061] 3. The device of the present invention can realize the integrated treatment of biogas slurry generated by anaerobic fermentation of the medicinal residues produced by the extraction of baicalin in the Scutellaria baicalensis processing factory, acidic waste liquid generated during the extraction of astragaloside, and biogas. It can achieve automatic control, is easy to operate, and is suitable for industrial production. Brief Description of the Drawings

[0062] Figure 1 is a schematic structural diagram of the comprehensive utilization system of waste in the Scutellaria baicalensis processing factory proposed by the present invention;

[0063] Figure 2 is a schematic structural diagram of the reaction tower of the present invention;

[0064] Figure 3 is a schematic structural diagram of the tail gas absorption tower of the present invention;

[0065] Figure 4 is a schematic structural diagram of the enrichment tower of the present invention;

[0066] Figure 5 is a schematic flow diagram of the comprehensive treatment method of waste in the Scutellaria baicalensis processing factory of the present invention. Detailed Embodiments

[0067] The following further describes the present invention with reference to embodiments.

[0068] The biogas slurry obtained after anaerobic fermentation of the medicinal residues collected from the Scutellaria baicalensis processing factory has the physical and chemical properties shown in Table 1. The acidic waste liquid (pH less than 2) generated by the water extraction and precipitation of Scutellaria baicalensis collected from the Scutellaria baicalensis processing factory, and the biomass ash residue is the residue after burning biomass waste (such as straw, bark and fruits and vegetables, etc.) at 900°C for 60 minutes, and the physical and chemical properties are shown in Table 2.

[0069] Table 1 Physical and Chemical Properties of Biogas Slurry

[0070]

[0071] Table 2 Physical and Chemical Properties of Biomass Ash Residue

[0072]

[0073]

[0074] Example 1 Preparation of Modified Biomass Filler of the Present Invention

[0075] (1) Add biomass ash residue to a ball mill, gradually spray acetic acid solution with a concentration of 20% during the ball milling process. The mass ratio of the acetic acid solution to the biomass ash residue is 1:30. Granulate to form spherical particles with a diameter of 5 - 8 mm, dry them, and increase the temperature from room temperature to 500 °C at a heating rate of 10 - 15 °C / min, then keep them at 500 °C for heat preservation and roasting for 1 - 2 h to obtain biomass ash residue particles. The ball mill is a commercially available WM2000 horizontal ball mill, with a rotational speed of 35 r / min for the ball mill cylinder, a motor power of 18.5 kW, and a processing capacity of 700 L / h.

[0076] (2) Wash the biomass ash residue particles obtained in step (1) with water, soak them for 24 h, then dry them in a forced-air drying oven at 105 °C, and place them in a tubular furnace. Under the protection of N 2 atmosphere, heat them to 900 °C at a heating rate of 10 °C / min and burn for 4 h;

[0077] (3) Immerse the biomass ash residue particles after roasting in step (2) in a mixed solution of 20% HNO 3 and 20% H 2 SO 4 (the volume ratio of the HNO 3 solution to the H 2 SO 4 solution is 2:1), perform ultrasonic treatment for 30 min, stir and heat for reflux oxidation in a water bath at 80 °C for 3 h, cool, and then repeatedly rinse with ultrapure water until the pH is neutral, and dry in a forced-air drying oven at 105 °C for 24 h until constant weight;

[0078] (4) According to a mass ratio of 1:10, place the biomass ash residue particles after drying in step (3) into an Fe 2 (NO) 3 solution, oscillate at 150 rpm for 24 h, then let it stand for 24 h, increase the temperature from room temperature to 500 °C at a heating rate of 10 °C / min, and keep it at 500 °C for heat preservation and roasting for 3 h to obtain modified biomass filler.

[0079] Example 2 Preparation of the modified biomass filler of the present invention

[0080] (1) Add biomass ash residue to a ball mill, gradually spray acetic acid solution with a concentration of 20% during the ball milling process. The mass ratio of the acetic acid solution to the biomass ash residue is 1:30. Granulate to form spherical particles with a diameter of 5 - 8 mm, dry them, and increase the temperature from room temperature to 500 °C at a heating rate of 10 - 15 °C / min, then keep them at 500 °C for heat preservation and roasting for 1 - 2 h to obtain biomass ash residue particles. The ball mill is a commercially available WM2000 horizontal ball mill, with a rotational speed of 35 r / min for the ball mill cylinder, a motor power of 18.5 kW, and a processing capacity of 700 L / h.

[0081] (2) Wash the biomass ash particles obtained in step (1) with water. After soaking for 24 h, dry them in a forced-air drying oven at 105 °C, then place them in a tubular furnace and sinter them at 900 °C for 4 h under the protection of N 2 atmosphere with a heating rate of 10 °C / min;

[0082] (3) Immerse the biomass ash particles sintered in step (2) in a mixed solution of 20% HNO 3 and 20% H 2 SO 4 (the volume ratio of the HNO 3 solution to the H 2 SO 4 solution is 2:1), perform ultrasonic treatment for 30 min, stir and heat under reflux in a water bath at 80 °C for 3 h, cool, and then repeatedly rinse with ultrapure water until the pH is neutral, and dry in a forced-air drying oven at 105 °C for 24 h until constant weight;

[0083] (4) Place the biomass ash particles dried in step (3) in a Fe 2 (NO) 3 solution at a mass ratio of 1:10, oscillate at 150 rpm for 24 h, then let it stand for 24 h, and heat from room temperature to 500 °C at a heating rate of 10 °C / min, and keep it at 500 °C for roasting for 3 h to obtain the modified biomass filler.

[0084] Example 3 Preparation of the modified biomass filler of the present invention

[0085] (1) Add biomass ash to a ball mill, and gradually spray a 20% acetic acid solution during the ball milling process. The mass ratio of the acetic acid solution to the biomass ash is 1:30, granulate to form spherical particles with a diameter of 5 - 8 mm, dry, and heat from room temperature to 500 °C at a heating rate of 10 - 15 °C / min, and keep it at 500 °C for roasting for 1 - 2 h to obtain biomass ash particles; the ball mill is a commercially available WM2000 horizontal ball mill, the rotational speed of the ball mill cylinder is 35 r / min, the motor power is 18.5 kW, and the processing capacity is 700 L / h.

[0086] (2) Wash the biomass ash particles obtained in step (1) with water. After soaking for 24 h, dry them in a forced-air drying oven at 105 °C, then place them in a tubular furnace and sinter them at 900 °C for 4 h under the protection of N 2 atmosphere with a heating rate of 10 °C / min;

[0087] (3) Immerse the biomass ash particles sintered in step (2) in a mixed solution of 20% HNO 3 and 20% H 2 SO 4 (the volume ratio of the HNO 3Solution and H 2 SO 4 (The volume ratio of the solution to H₂SO₄ solution is 2:1), ultrasonic treatment for 30 min, stirring and heating under reflux oxidation in a water bath at 80 °C for 3 h, after cooling, repeatedly rinsing with ultrapure water until the pH is neutral, and drying in a forced-air drying oven at 105 °C for 24 h until constant weight;

[0088] (4) According to the mass ratio of 1:10, place the biomass ash residue particles dried in step (3) into Fe 2 (NO) 3 solution, oscillate at 150 rpm for 24 h, then stand still for 24 h, heat from room temperature to 500 °C at a heating rate of 10 °C / min, and calcine at 500 °C for 3 h to obtain the modified biomass filler.

[0089] Example 4 Comprehensive treatment system for waste from Scutellaria baicalensis processing factory

[0090] The comprehensive treatment system for waste from Scutellaria baicalensis processing factory is shown in Figures 1-4 and specifically includes:

[0091] It includes a reaction tower (1), a feeding device (2), a tail gas absorption tower (3) and an enrichment tower (33);

[0092] At the top of the reaction tower (1), a feeding pipeline (8) and an exhaust pipeline (15) are fixedly connected. The feeding pipeline (8) is connected to the feeding device (2), and a feeding pump (28), a feeding solenoid valve (7) and an exhaust check valve (17) are fixedly installed. The first exhaust pipeline (15) is connected to the tail gas absorption tower (3), and a first exhaust solenoid valve (16) is fixedly installed;

[0093] At the bottom of the reaction tower (1), an air inlet pipeline (13) is fixedly connected. The air inlet pipeline (13) is fixedly installed with an air inlet solenoid valve (12), and the air inlet pipeline (13) is externally connected to a blower (11);

[0094] At the bottom side of the reaction tower (1), a drainage pipeline (27) is fixedly connected. The drainage pipeline (27) is fixedly installed with a drainage solenoid valve (26); the drainage pipeline (27) is connected to a reflux valve (32) and an enrichment tower (33), and the reflux valve (32) is installed on a reflux pipeline (31).

[0095] At the inner top of the reaction tower (1), a water distributor (101) is fixedly installed. At the upper part inside the reaction tower (1), a first mesh partition (104) is fixedly installed, and at the lower part, a second mesh partition (102) is fixedly installed. The first packing layer (103) is placed in the space between the first mesh partition and the second mesh partition. At the outer top of the reaction tower (1), a pressure relief pipeline (29) is fixedly installed, and the pressure relief pipeline (29) is fixedly installed with a pressure relief valve (30).

[0096] A liquid level gauge (14) is fixedly installed at the top inside the reaction tower (1). The packing is modified biomass ash particles (103).

[0097] A touch all-in-one machine (25) is installed on one side of the reaction tower (1). The touch all-in-one machine (25) is respectively connected to a feed solenoid valve (7), a blower (11), an intake solenoid valve (12), a liquid level gauge (14), an exhaust solenoid valve (16), an exhaust solenoid valve (18), a gas monitor (19), an acid liquid circulation pump (20), a pH monitor (21), a drain solenoid valve (26), a feed pump (28), a pressure relief valve (30), a reflux valve (32), a biogas exhaust solenoid valve (36), and a biogas slurry circulation pump (38).

[0098] A water inlet pipeline (10) is fixedly installed on one side of the feeding device (2). A screw mixer (5) is installed inside the feeding device (2), and a material bin (6) is fixedly installed at the top. The material bin (6) is equipped with a motor (9) to control the screw mixer (5) inside the material bin; a control panel (4) is fixedly installed at the top of the feeding device (2), and the control panel (4) is respectively connected to the motor (9) and the screw mixer (5).

[0099] An acid liquid circulation water tank (301) is arranged at the bottom inside the tail gas absorption tower (3). A pH monitor (21) is fixedly installed on the acid liquid circulation water tank (301). The acid liquid circulation water tank (301) is externally connected to an acid liquid circulation pipeline (23). An acid liquid circulation pump (20) is fixedly installed on the acid liquid circulation pipeline (23). The acid liquid circulation pump (20) is connected to the spraying area through an acid liquid spraying pipeline (22); an acid liquid spraying head (303) is fixedly installed at the bottom of the spraying pipeline (22) inside the tail gas absorption tower (3); a second packing layer (302) is fixedly installed inside the tail gas absorption tower (3); a cyclone mist eliminator (304) is fixedly installed at the top inside the tail gas absorption tower (3).

[0100] A second exhaust pipeline (24) is fixedly installed at the top outside the tail gas absorption tower (3). A gas monitor (19) and a second exhaust solenoid valve (18) are fixedly installed on the second exhaust pipeline (24).

[0101] A biogas slurry circulation water tank (331) is arranged at the bottom inside the enrichment tower (33). The biogas slurry circulation water tank (331) is externally connected to a biogas slurry circulation pipeline (37). A biogas slurry circulation pump (38) is fixedly installed on the biogas slurry circulation pipeline (37). The biogas slurry circulation pump (38) is connected to the spraying area through a biogas slurry spraying pipeline (37); a biogas slurry spraying head (332) is fixedly installed on the spraying pipeline inside the enrichment tower (33); a third packing layer (333) is fixedly installed inside the enrichment tower (33).

[0102] A biogas inlet pipeline (34) is fixedly installed at the outer bottom of the enrichment tower (33), and a biogas exhaust pipeline (35) is fixedly installed at the top. A biogas exhaust solenoid valve (36) is fixedly installed on the biogas exhaust pipeline (35). A liquid discharge pipeline (39) is fixedly installed at the bottom of the enrichment tower (33), and a liquid discharge solenoid valve (40) is fixedly installed on the liquid discharge pipeline (39).

[0103] Example 5 Comprehensive treatment method for waste from Scutellaria baicalensis processing factory of the present invention

[0104] The flow chart of the comprehensive treatment method for waste from Scutellaria baicalensis processing factory of the present invention is shown in Figure 5 . The fillers of the first packing layer (103), the second packing layer (302), and the third packing layer (333) are all the modified biomass fillers of Example 1.

[0105] (1) 10 tons of biogas slurry to be treated flows into the feeding device (2) through the water inlet pipeline (10). At the same time, the screw mixer (5) fixedly installed in the feeding device (2) is started, and the motor (9) fixedly installed at the top of the feeding device (2) is started to control the rotation of the screw in the material bin. 0.2 tons of biomass ash in the material bin (6) falls into the feeding device (2) along with the rotating screw. Under the action of the screw mixer (5), the biogas slurry and the biomass ash are fully mixed at a rotation speed of 100 rpm to obtain a mixed liquid;

[0106] (2) The feeding pump (28) and the feeding solenoid valve (7) are opened, and the air inlet solenoid valve (12), the exhaust solenoid valve (16), and the drain solenoid valve (26) are closed. The mixed liquid in step (1) flows into the reaction tower (1) through the feeding pipeline (8) and the exhaust check valve (17), and flows through the first packing layer (103). When the feeding liquid level rises to the stop liquid level set by the liquid level gauge (14), the air inlet solenoid valve (12), the blower (11), and the exhaust solenoid valve (16) are opened to start ammonia stripping by aeration. The aeration intensity is 180 m 3 / (m 2 ·h), and the stripping time is 30 min. The drain solenoid valve (26) and the pressure relief valve (30) are opened, and the air inlet solenoid valve (12) and the exhaust solenoid valve (16) are closed. The biogas slurry after aeration treatment is discharged through the drain pipeline (27). 50% of it is refluxed to the hydrolysis acidification tank of the front-end anaerobic fermentation process, and the remaining part flows into the enrichment tower (33); The tail gas after aeration treatment enters the tail gas absorption tower (3) through the exhaust pipeline (15);

[0107] (3) Load 40 tons of acidic waste liquid to be treated into the acid liquid circulation water tank (301), start the exhaust solenoid valve (18) and the acid liquid circulation pump (20). The acidic waste liquid is sprayed out by the spray head (303) through the acid liquid circulation pipeline (23), the acid liquid circulation pump (20) and the spray pipeline (22). After contacting the tail gas entering the tail gas absorption tower (3) through the exhaust pipeline (15) on the surface of the second packing layer (302), it flows into the lower acid liquid circulation water tank for reuse. When the pH monitor (21) fixedly installed on one side of the acid liquid circulation water tank (301) shows that the pH of the acidic waste liquid > 6, it is discharged to obtain treatment liquid 1. The remaining tail gas rises to the cyclone mist eliminator (304), and after being monitored by the gas monitor (19), it is discharged.

[0108] (4) The biogas slurry after the aeration treatment in step (2) flows into the enrichment tower (33). The biogas generated by the anaerobic fermentation system enters the enrichment tower through the biogas inlet pipeline (34). At the same time, open the biogas exhaust solenoid valve (36), the biogas slurry circulation pump (38) and the drain solenoid valve (40). The biogas slurry is sprayed into the enrichment tower through the biogas slurry spray head (332) to contact the biogas, and the biogas slurry absorbing H 2 S is discharged through the drain pipeline (39) to obtain treatment liquid 2; after the biogas passes through the third packing layer (333), the desulfurized biogas is discharged through the biogas exhaust pipeline and collected for power generation;

[0109] Treatment liquid 1 and treatment liquid 2 are compounded at a volume ratio of 1:1 to prepare a water-soluble fertilizer, which can meet the water-soluble fertilizer standard of agricultural biogas slurry (GB / T40750-2021) (see Table 3) and be reused in farmland;

[0110] Table 3

[0111]

[0112]

[0113] The H 2 S content in the biogas after the enrichment tower treatment meets the biogas quality requirements for power generation in the Technical Code for Large and Medium-sized Biogas Projects (GB / T 51063-2014) (see Table 4), and can be reused for power generation by biogas generators or for combustion heating in biogas boilers.

[0114] Table 4 H 2 S concentration

[0115]

[0116] The above description of the specific embodiments of the present invention does not limit the present invention. Those skilled in the art can make various changes or deformations according to the present invention. As long as they do not depart from the spirit of the present invention, they shall fall within the scope protected by the claims of the present invention.

Claims

1. A comprehensive treatment system for waste from a scutellaria processing plant, comprising a reaction tower (1), a feeding device (2), a tail gas absorption tower (3) and an enrichment tower (33); The top of the reaction tower (1) is fixedly connected with a feed pipeline (8) and an exhaust pipeline. (15), the feed pipeline (8) is connected to the feed device (2), and is fixedly installed with a feed pump (28), a feed solenoid valve (7) and an exhaust check valve (17); the first exhaust pipeline (15) is connected to the tail gas absorption tower (3), and is fixedly installed with a first exhaust solenoid valve (16); An air intake pipeline (13) is fixedly connected to the bottom of the reaction tower (1), an air intake solenoid valve (12) is fixedly installed on the air intake pipeline (13), and the air intake pipeline (13) is externally connected to a blower (11); A drainage pipeline (27) is fixedly connected to the bottom side of the reaction tower (1), and a drainage solenoid valve (26) is fixedly installed on the drainage pipeline (27); the drainage pipeline (27) is connected to a reflux valve (32) and an enrichment tower (33), and the reflux valve (32) is installed on the reflux pipeline (31).

2. The system as claimed in claim 1, wherein a water distributor (101) is fixedly installed on the top of the reaction tower (1), a first mesh partition (104) is fixedly installed on the upper part of the reaction tower (1), a second mesh partition (102) is fixedly installed on the lower part, a first packing layer (103) is placed in the space between the first mesh partition and the second mesh partition, a pressure relief pipeline (29) is fixedly installed on the top of the outside of the reaction tower (1), and a pressure relief valve (30) is fixedly installed on the pressure relief pipeline (29).

3. According to the system according to any one of claims 1 to 2, a touch all-in-one machine (25) is installed on one side of the reaction tower (1), and the touch all-in-one machine (25) is respectively connected to the feed solenoid valve (7), the blower (11), the air intake solenoid valve (12), the liquid level meter (14), the exhaust solenoid valve (16), the exhaust solenoid valve (18), the gas monitor (19), the acid circulation pump (20), the pH monitor (21), the drain solenoid valve (26), the feed pump (28), the pressure relief valve (30), the reflux valve (32), the biogas exhaust solenoid valve (36) and the biogas liquid circulation pump (38).

4. A system according to any one of claims 1 to 3, wherein an acid liquid circulating water tank (301) is arranged at the bottom of the tail gas absorption tower (3), a pH monitor (21) is fixedly installed on the acid liquid circulating water tank (301), an acid liquid circulating pipeline (23) is externally connected to the acid liquid circulating water tank (301), an acid liquid circulating pump (20) is fixedly installed on the acid liquid circulating pipeline (23), and the acid liquid circulating pump (20) is connected to the spraying area through an acid liquid spraying pipeline (22); an acid liquid spray head (303) is fixedly installed at the bottom of the spraying pipeline (22) in the tail gas absorption tower (3); a second packing layer (302) is fixedly installed in the tail gas absorption tower (3); and a cyclone demister (304) is fixedly installed at the top of the tail gas absorption tower (3).

5. The system according to any one of claims 1 to 4, wherein a biogas slurry circulating water tank (331) is arranged at the bottom of the enrichment tower (33), the biogas slurry circulating water tank (331) is externally connected to a biogas slurry circulating pipeline (37), the biogas slurry circulating pipeline (37) is fixedly provided with a biogas slurry circulating pump (38), and the biogas slurry circulating pump (38) is connected to a spraying area through a biogas slurry spraying pipeline (37); a biogas slurry spray head (332) is fixedly provided on the spraying pipeline in the enrichment tower (33); and a third packing layer (333) is fixedly provided in the enrichment tower (33).

6. The system according to any one of claims 1 to 5, wherein a biogas inlet pipeline (34) is fixedly installed at the bottom of the outer side of the enrichment tower (33), a biogas exhaust pipeline (35) is fixedly installed at the top, a biogas exhaust solenoid valve (36) is fixedly installed on the biogas exhaust pipeline (35), and a drainage pipeline (39) is fixedly installed at the bottom of the enrichment tower (33), and a drainage solenoid valve (40) is fixedly installed on the drainage pipeline (39).

7. A comprehensive treatment method for waste from a scutellaria processing plant, wherein the waste includes acidic waste liquid generated by water extraction and precipitation of scutellaria and biogas slurry generated by anaerobic fermentation of scutellaria extraction residues, and the treatment of the waste specifically comprises the following steps: (1) The biogas slurry to be treated flows into the feeding device (2) through the water inlet pipe (10), and at the same time, the spiral mixer (5) fixedly installed in the feeding device (2) is started. (2) The motor (9) fixed on the top is started to control the screw in the material bin to rotate, and the biomass ash in the material bin (6) falls into the feeding device (2) along with the rotating screw. The biogas slurry and the biomass ash are fully mixed under the action of the spiral mixer (5) to obtain a mixed liquid; (2) Open the feed pump (28) and the feed solenoid valve (7), and close the air intake solenoid valve (12), an exhaust solenoid valve (16) and a drain solenoid valve (26), the mixed liquid of step (1) flows into the reaction tower (1) through the feed pipeline (8) and the exhaust check valve (17), flows through the first packing layer (103), and when the feed liquid level rises to the stop liquid level set by the liquid level meter (14), the intake solenoid valve (12), the blower (11), the exhaust solenoid valve (26) are opened. (16) Start aeration to remove ammonia; open the drainage solenoid valve (26) and the pressure relief valve (30), close the air inlet solenoid valve (12) and the exhaust solenoid valve (16), and the aerated biogas slurry is discharged through the drainage pipeline (27) and flows into the enrichment tower (33); the exhaust gas after aeration enters the exhaust gas absorption tower (3) through the exhaust pipeline (15); (3) The acidic waste liquid to be treated is loaded into the acid liquid circulation water tank (301) arranged at the bottom of the tail gas absorption tower (3), and the exhaust solenoid valve (18) and the acid liquid circulation pump are started. (20), the acid waste liquid is sprayed out from the spray head (303) through the acid liquid circulation pipeline (23), the acid liquid circulation pump (20) and the spray pipeline (22), and contacts with the tail gas entering the tail gas absorption tower (3) through the exhaust pipeline (15) in step (2) on the surface of the second packing layer (302), and the treated liquid flows into the acid liquid circulation water tank at the bottom for continuous reuse, and the remaining tail gas rises to the cyclone demister (304) and is discharged after being monitored by the gas monitor (19); (4) The biogas slurry after aeration treatment in step (2) flows into the enrichment tower (33), and the biogas generated by the anaerobic fermentation system enters the enrichment tower through the biogas inlet pipeline (34), and the biogas exhaust solenoid valve (36), the biogas slurry circulation pump (38) and the liquid discharge solenoid valve (40) are opened at the same time. The biogas slurry is sprayed into the enrichment tower through the biogas spray head (332) to contact with the biogas, absorb H2S in the biogas, and is discharged through the drainage pipeline (39) to obtain the treated liquid 2, which is used for the subsequent production and processing of organic liquid fertilizer. After the biogas passes through the third packing layer (333), the desulfurized biogas is discharged through the biogas exhaust pipeline for power generation.

8. The method according to claim 7, wherein the fillers of the first filler layer (103), the second filler layer (302), and the third filler layer (333) are all modified biomass fillers.

9. A modified biomass filler, the preparation method of which comprises the following steps: (1) adding biomass ash into a ball mill, gradually spraying an acetic acid solution with a concentration of 20-30% during the ball milling process, wherein the mass ratio of the acetic acid solution to the biomass ash is 1:30-50, granulating into spherical particles of 5-8 mm, drying, heating from room temperature to 400-500° C. at a rate of 10-15° C. / min, and calcining at 400-500° C. for 1-2 h to obtain biomass ash particles; (2) washing the biomass ash particles obtained in step (1) with water, soaking for 24-48 hours and then drying, heating the temperature from room temperature to 800-900° C. at a rate of 10-15° C. / min under nitrogen protection, and calcining at 800-900° C. for 4-6 hours; (3) immersing the biomass ash particles fired in step (2) in a mixed solution of 20% HNO3 and 20% H2SO4, ultrasonically treating for 30-60 min, stirring, heating, refluxing and oxidizing in a 70-80°C water bath for 3-4 h, cooling, and repeatedly rinsing with ultrapure water until the pH is neutral, and drying to constant weight; (4) placing the biomass ash particles dried in step (3) in a Fe2(NO)3 solution at a mass ratio of 1:10-20, shaking at 100-150 rpm for 12-24 hours, then standing for 24 hours, heating from room temperature to 400-500°C at a heating rate of 10-15°C / min, and calcining at 400-500°C for 3-4 hours to obtain the product.

10. Use of the modified biomass filler according to claim 9 in water treatment.

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