A movable prizing type unpowered mine tunnel antimony-containing water treatment system and method

Abstract

The application discloses a movable pry-mounted non-powered mine tunnel antimony-containing water gushing treatment system and method, the system comprises a plurality of warehouse bodies arranged side by side, and the warehouse bodies are sequentially a buffer homogenizing warehouse, a sedimentation warehouse, an adsorption treatment warehouse and a clean water buffer warehouse; the warehouse bodies are relatively arranged in an up-down sliding mode and are fixedly connected through a connecting rod located at the top; the method comprises the following steps: S1, preparation work; S2, hoisting and positioning; and S3, continuous water treatment; the system is integrally arranged in a standard container pry-mounted module, can be quickly deployed to any water gushing point accessible by road through road transportation, is driven by gravity generated by natural terrain difference throughout the journey, does not need external power supply and is perfectly suitable for mine areas without power supply.

Description

Technical Field

[0001] This invention relates to the field of mine water treatment technology, specifically to a mobile skid-mounted, non-powered mine antimony-containing inflow water treatment system and method. Background Technology

[0002] Mine water inflow is a common environmental problem in mineral resource extraction, especially in antimony mines, where the inflow often contains high concentrations of dissolved antimony Sb(III) and Sb(V), exhibiting strong biotoxicity and high environmental risks. Current treatment technologies, such as chemical precipitation and membrane separation, while effective, generally suffer from three major drawbacks: high energy consumption (reliant on continuous electricity), high maintenance costs (requiring reagent addition and dedicated personnel), and high costs (large investments in fixed infrastructure). This makes them virtually unusable in remote, power-deficient, dispersed, or short-service-life mining areas.

[0003] Furthermore, mine water inflow points often change with the mining process, and traditional fixed treatment facilities, once built, are difficult to relocate, resulting in poor flexibility. Existing non-powered water treatment devices mostly focus on domestic sewage or simple filtration, lacking the ability to specifically remove heavy metals like antimony; while mobile water treatment equipment largely relies on external power supply, making it difficult to meet the needs of green governance in mines. Existing methods do indeed face many problems and challenges in practical applications. Due to the special environment of mines, water flow and quality fluctuate greatly, treatment sites are limited, and the underground environment is humid and highly corrosive, placing extremely high demands on equipment durability. This results in poor equipment adaptability, short lifespan, difficult maintenance, unstable treatment effects, high operating costs, low overall efficiency, and environmental risks.

[0004] In current research, some researchers have conducted in-depth studies on this topic, such as developing gravity-based non-powered facilities that utilize the gravity of gushing water to treat it from top to bottom. For example, the invention patent with patent authorization announcement number CN117509806B discloses a non-pressurized mountain mine tunnel contaminated water remediation system, which includes the mine mountain, the mine tunnel water outlet on the mountain, and a gully formed along the mountain's contour. The gully is located downstream of the mine tunnel water outlet. In the gully, the mine tunnel water collection pools and at least one-stage sewage treatment device are arranged sequentially from high to low elevation. Each stage of sewage treatment device includes a remediation device and a monitoring pool connected to the downstream end of the remediation device. The monitoring pool is equipped with a qualified water outlet that directly discharges into the gully and a non-standard water outlet that flows into the remediation device of the next stage of sewage treatment device. Both the qualified water outlet and the non-standard water outlet are equipped with electric valves. The technology claims that it can utilize the potential energy of polluted water to flow through the remediation device without the need for an additional power source. Moreover, multi-stage remediation and monitoring ensure thorough remediation while avoiding unnecessary waste of remediation materials, thus achieving the technical effect of rationally using remediation materials according to the pollutant content.

[0005] However, the above-mentioned technologies and similar products in the prior art still have some drawbacks: no adjustment or homogenization unit is mentioned, such as a homogenization tank. The flow rate, antimony concentration, and pH value of mine water fluctuate greatly. Directly entering the chromatography column with fixed packing can easily lead to unstable treatment effect, premature penetration or poisoning failure of the packing. Moreover, it is extremely impractical to fill and replace loose packing in long pipelines, and construction and maintenance will be extremely difficult. The "segmented filling frame" and "limiting rib" designs mentioned in the above patents are too idealistic and cannot solve the fundamental problem of how to remove the packing after it is compacted and blocked. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a mobile skid-mounted, non-powered mine antimony-containing water treatment system and method.

[0007] The technical solution of this invention is: A mobile skid-mounted, non-powered mine antimony-containing water treatment system includes several compartments arranged side by side, namely a buffer homogenization compartment, a sedimentation compartment, an adsorption treatment compartment, and a clear water buffer compartment. The compartments are slidably arranged vertically relative to each other. The compartments are fixedly connected by a connecting rod located at the top. When the compartments are hoisted and positioned as needed, the connecting rod can be pulled out to change the compartments from a fixed state to a sliding state. The buffer homogenization chamber is equipped with a water inlet hose at the front end, and the chambers are connected to each other by a detachable water guide hose. The sedimentation chamber is equipped with several inclined sedimentation components for sedimentation to remove suspended solids; The adsorption treatment chamber is equipped with several adsorption filter tanks connected in series. Each adsorption filter tank is equipped with composite packing material, which includes FeOOH@BC particles and inert support particles. The filling rate of the composite packing material in the adsorption filter tank is 60-80%. The clear water buffer tank is equipped with a siphon drain; Each compartment has an interface for installing the water guide hose at the bottom rear side and the top front side, and each water guide hose is equipped with a valve.

[0008] Furthermore, in the composite packing, the mass ratio of FeOOH@BC particles to inert support particles is 1:25~35, the inert support particles are quartz sand, the inclined sedimentation assembly includes 15~30 inclined plates or inclined tubes, and the adsorption filter tanks are 3~5.

[0009] Note: By reasonably setting the number of adsorption filter tanks, inclined plates or inclined tubes, high sedimentation efficiency and adsorption efficiency can be maintained, and can be adjusted according to the amount of water flow.

[0010] Furthermore, the preparation method of the FeOOH@BC particles is as follows: add biochar and β-FeOOH powder to a grinding container, wherein the mass ratio of β-FeOOH powder to biochar is 2~4:1, put in an agate ball, set the rotation speed to 300~400 rpm, and continue grinding for 6~10 hours, stopping for 5~15 minutes every 15~30 minutes to obtain FeOOH@BC particles.

[0011] Note: The FeOOH@BC particle adsorption packing material, specifically designed for this system, has a strong and specific adsorption effect on antimony ions, ensuring that the antimony concentration in the effluent consistently meets the discharge standards.

[0012] Preferably, the preparation method of the biochar is as follows: the biomass raw material is washed with pure water and dried at 55~65℃ for 72h, filled into a quartz boat and placed in a high-temperature tube furnace, N2 is introduced and maintained for 20~40min to remove air from the furnace, the heating rate is set to 8~14℃ / min, and the temperature is heated to 300±5℃ and maintained for 2h±5min. N2 is introduced as a protective gas throughout the preparation process, and the biomass raw material is straw.

[0013] Note: By further refining the biochar preparation method, it can be ensured that the prepared composite filler has high comprehensive performance.

[0014] Furthermore, the outer walls of each compartment are connected by slide rails and sliders. The sliders and slide rails are T-shaped and matched with each other. In two adjacent compartments, the slide rail is located on the corresponding front compartment and the slider is located on the corresponding rear compartment. Each compartment has a slot at the top and the connecting rod passes through each slot.

[0015] Explanation: By setting up slide rails and sliders, the two chambers can slide together to create a height difference, effectively utilizing the gravity of the gushing water to achieve continuous processing without power.

[0016] Furthermore, each of the slots has a limiting hole on its side wall, and the connecting rod has a limiting groove at the location of each limiting hole. The limiting groove and the limiting hole are connected by a limiting pin.

[0017] Note: Limiting pins maintain the stability of each compartment as a whole, while also facilitating disassembly and assembly.

[0018] Furthermore, each of the slots is provided with a lifting ring at the top, and each of the compartments is provided with several telescopic support legs at the bottom.

[0019] Note: The lifting rings and telescopic outriggers facilitate on-site installation and positioning.

[0020] This invention also provides a mobile skid-mounted, non-powered mine antimony-containing water inflow treatment method, based on the above-mentioned mobile skid-mounted, non-powered mine antimony-containing water inflow treatment system, comprising the following steps: S1. Preparation: Prepare the composite filler and fill it into the adsorption filter tank. Place each of the chambers side by side and connect them through the connecting rod. Install limiting pins on the first and last slots so that the whole system can be hoisted as a whole. S2. Lifting and Positioning: Locate the downstream position of the antimony-containing water inflow point in the mine to be treated. Lift the first and last lifting rings and lift the system to this position. Align the water inlet hose with the water inflow point. Extend the telescopic support legs at the bottom of the buffer homogenization chamber and insert them into the slope soil to keep the buffer homogenization chamber fixed. Then change the lifting position to the lifting rings of the sedimentation chamber and the clear water buffer chamber. At the same time, change the position of the limiting pin to the slots of the sedimentation chamber and the clear water buffer chamber. At this time, keep it in the lifting state and lower it so that the slider of the sedimentation chamber slides in the slide rail of the buffer homogenization chamber until the sedimentation chamber reaches the designated position. Then extend the telescopic support legs of the sedimentation chamber and insert them into the slope soil to keep the sedimentation chamber fixed. After that, complete the fixing and positioning of the adsorption treatment chamber and the clear water buffer chamber in sequence according to the above method. Install water guide hoses at each joint. S3. Continuous water treatment: Antimony-containing inflow water from the mine enters the buffer homogenization chamber through the inlet hose. After homogenization, it is guided to the sedimentation chamber through the water guide hose under the action of gravity and siphon. After sedimentation removes suspended solids, it is guided to the adsorption treatment chamber through the water guide hose under the action of gravity and siphon. After being adsorbed by each of the adsorption filter tanks in sequence, it is guided to the clear water buffer chamber through the water guide hose under the action of gravity and siphon, and then discharged through the siphon drainer.

[0021] Furthermore, in S3, the total hydraulic retention time is 0.5~2h, and the water quality inside the clear water buffer tank is sampled and monitored every 0.5~1h. The initial total hydraulic retention time is set to 1h. When the antimony mass concentration exceeds 0.015mg / L, the total hydraulic retention time is increased by 10~20%, and when the antimony mass concentration is less than 0.005mg / L, the total hydraulic retention time is shortened by 10~20%.

[0022] Note: By adjusting the number of adsorption filter tanks, the total hydraulic retention time can be reasonably adjusted to ensure the best water treatment effect while reducing the consumption of internal adsorption materials and achieving the best economic benefits.

[0023] The beneficial effects of this invention are: This invention discloses a mobile skid-mounted, non-powered mine antimony-containing water treatment system and method, aiming to effectively solve the problems of high energy consumption (reliant on continuous power), high maintenance costs (requiring reagent addition and dedicated personnel management), high costs (large investment in fixed facilities), and low efficiency (poor antimony adsorption and removal performance) of traditional mine antimony-containing water treatment technologies. It has the advantages of high-efficiency antimony removal, zero-energy operation, rapid and flexible deployment, and low maintenance costs, as detailed below: 1. "Ready to use and zero-energy operation: The system is integrated into a standard container skid-mounted module and can be quickly deployed to any water inflow point accessible by road. It is driven solely by gravity generated by the natural elevation difference of the terrain and does not require an external power source, making it perfectly suited for mining areas without power supply. 2. Targeted and efficient antimony removal: The core of the system adopts an adsorption module of iron hydroxyl oxide modified biochar (FeOOH@BC). This material has a specific and strong adsorption effect on antimony ions, which can ensure that the antimony concentration in the effluent is stable and meets the discharge standards. 3. High degree of modularity and ease of maintenance: Quick Replacement: The core adsorption unit is designed as a standardized adsorption filter canister. Once saturated, it can be quickly replaced as a whole, just like replacing a battery, without shutting down the system, which greatly simplifies maintenance operations. Centralized regeneration: Saturated adsorption filter tanks can be centrally transported back to the treatment center for professional regeneration or resource recycling, reducing on-site operation difficulties and environmental risks; 4. Strong adaptability to terrain and working conditions: Equipped with hydraulic leveling telescopic outriggers and flexible water guiding hoses, each compartment can slide up and down to form a height difference, which can adapt to uneven site terrain. The processing capacity can be flexibly expanded by connecting multiple skid-mounted modules in parallel to meet different needs from small flow seepage to large flow surge. 5. Significant economic benefits: It eliminates the need for fixed civil engineering, permanent power distribution facilities and daily chemical consumption. The main costs are concentrated on one-time equipment investment and periodic replacement of adsorption modules, resulting in a significant reduction in overall operating costs. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the overall structure of a mobile skid-mounted, non-powered mine antimony-containing water treatment system according to the present invention. Figure 2 This is a schematic diagram of the internal structure of a mobile skid-mounted, non-powered mine antimony-containing water treatment system according to the present invention. Figure 3 This is a schematic diagram of the structure of a mobile skid-mounted, non-powered mine antimony-containing water inflow treatment system of the present invention during the initial installation. Figure 4 This is a top view of a mobile skid-mounted, non-powered mine antimony-containing water treatment system according to the present invention; Figure 5This is a cross-sectional view of the connection between the slider and the slide rail in a movable skid-mounted non-powered mine antimony-containing water treatment system of the present invention. Figure 6 This is a cross-sectional view of the limiting pin in a movable skid-mounted, non-powered mine antimony-containing water treatment system of the present invention. Figure 7 a and b are SEM images of biochar at different magnifications in the experimental example; Figure 7 c and d are SEM images of the composite material (BM-β-FeOOH / BC) at different magnifications in the experimental example.

[0025] Among them, 1-tank body, 11-buffer homogenization tank, 111-inlet hose, 12-sedimentation tank, 121-tilted sedimentation component, 13-adsorption treatment tank, 131-adsorption filter tank, 14-clear water buffer tank, 141-siphon drainer, 15-interface, 16-slide rail, 17-slider, 18-telescopic support leg, 2-connecting rod, 21-limiting groove, 3-water guide hose, 4-slot, 41-limiting hole, 42-lifting ring, 5-limiting pin. Detailed Implementation

[0026] Example 1: A mobile skid-mounted, non-powered mine antimony-containing water treatment system, such as... Figure 1 As shown, it includes several chambers 1 arranged side by side, namely buffer homogenization chamber 11, sedimentation chamber 12, adsorption treatment chamber 13, and clear water buffer chamber 14. Each chamber 1 is slidably arranged vertically relative to each other, and each chamber 1 is fixedly connected by a connecting rod 2 located at the top. like Figure 1 As shown, the buffer homogenization chamber 11 is equipped with a water inlet hose 111 at the front end, and each chamber 1 is connected by a detachable water guide hose 3. The buffer homogenization chamber 11 is a commercially available RCH series inclined bottom homogenization chamber. like Figure 2 As shown, the sedimentation chamber 12 is equipped with several inclined sedimentation components 121 for sedimentation to remove suspended solids. The inclined sedimentation components 121 include 20 inclined plates. like Figure 2 As shown, the adsorption treatment chamber 13 is equipped with three adsorption filter tanks 131 connected in series. Each adsorption filter tank 131 is equipped with composite packing material, which includes FeOOH@BC particles and inert support particles. The filling rate of the composite packing material in the adsorption filter tank 131 is 75%. In the composite packing material, the mass ratio of FeOOH@BC particles to inert support particles is 1:30. The inert support particles are quartz sand. The preparation method of FeOOH@BC particles is as follows: add biochar and β-FeOOH powder to a grinding container, wherein the mass ratio of β-FeOOH powder to biochar is 3:1, put in agate balls, set the rotation speed to 350 rpm, and continue grinding for 8 hours. Stop for 10 minutes every 20 minutes of rotation to obtain FeOOH@BC particles. The preparation method of biochar is as follows: the biomass raw material is washed with pure water and dried at 60℃ for 72h. It is then filled into a quartz boat and placed in a high-temperature tube furnace. N2 is introduced and kept for 30min to remove the air in the furnace. The heating rate is set to 10℃ / min. After heating to 300℃, it is kept for 2hmin. N2 is introduced as a protective gas throughout the preparation process. The biomass raw material is straw. like Figure 2 As shown, the clear water buffer tank 14 is equipped with a siphon drainer 141. A commercially available water quality probe is used inside the clear water buffer tank 14 to monitor the antimony concentration. The siphon drainer 141 is a commercially available TY series siphon drainer. like Figures 3-6 As shown, each compartment 1 has an interface 15 for installing a water guide hose 3 at the bottom rear side and the top front side. Each water guide hose 3 is equipped with a valve. The outer walls of each compartment 1 are connected by a slide rail 16 and a slider 17. The slider 17 and the slide rail 16 are mutually matched T-shaped. In two adjacent compartments 1, the slide rail 16 is located on the corresponding front compartment 1, and the slider 17 is located on the corresponding rear compartment 1. Each compartment 1 has a slot 4 at the top. The connecting rod 2 passes through each slot 4. Each slot 4 has a limiting hole 41 on its side wall. The connecting rod 2 has a limiting groove 21 at the position of each limiting hole 41. The limiting groove 21 and the limiting hole 41 are connected by a limiting pin 5. Each slot 4 has a lifting ring 42 at the top. Each compartment 1 has several telescopic support legs 18 at the bottom. The telescopic support legs 18 are commercially available spiral jacks.

[0027] Example 2: The difference between this example and Example 1 is that there are 4 adsorption filter tanks 131.

[0028] Example 3: The difference between this example and Example 1 is that there are 5 adsorption filter tanks 131.

[0029] Example 4: The difference between this example and Example 1 is that the inclined sedimentation assembly 121 includes 16 inclined plates.

[0030] Example 5: The difference between this example and Example 1 is that the inclined sedimentation assembly 121 includes 18 inclined plates.

[0031] Example 6: The difference between this example and Example 1 is that the inclined sedimentation assembly 121 includes 25 inclined tubes.

[0032] Example 7: The difference between this example and Example 1 is that the inclined sedimentation assembly 121 includes 30 inclined tubes.

[0033] Example 8: The difference between this example and Example 1 is that the filling rate of the composite packing in the adsorption filter tank 131 is 60%, and the mass ratio of FeOOH@BC particles to inert support particles in the composite packing is 1:25.

[0034] Example 9: The difference between this example and Example 1 is that the filling rate of the composite packing in the adsorption filter tank 131 is 70%, and the mass ratio of FeOOH@BC particles to inert support particles in the composite packing is 1:28.

[0035] Example 10: The difference between this example and Example 1 is that the composite packing has a filling rate of 80% in the adsorption filter tank 131, and the mass ratio of FeOOH@BC particles to inert support particles in the composite packing is 1:35.

[0036] Example 11: The difference between this example and Example 1 is that the preparation method of FeOOH@BC particles is as follows: biochar and β-FeOOH powder are added to a grinding container, wherein the mass ratio of β-FeOOH powder to biochar is 4:1, agate balls are placed in, the rotation speed is set to 400 rpm, and grinding is continued for 10 hours. FeOOH@BC particles are obtained by stopping for 15 minutes every 30 minutes of rotation. The preparation method of biochar is as follows: the biomass raw material is washed with pure water and dried at 55℃ for 72h. It is then filled into a quartz boat and placed in a high-temperature tube furnace. N2 is introduced and kept for 20min to remove the air in the furnace. The heating rate is set to 8℃ / min. After heating to 295℃, it is kept for 1h+55min. N2 is introduced as a protective gas throughout the preparation process. The biomass raw material is straw.

[0037] Example 12: The difference between this example and Example 1 is that the preparation method of FeOOH@BC particles is as follows: biochar and β-FeOOH powder are added to a grinding container, wherein the mass ratio of β-FeOOH powder to biochar is 2:1, agate balls are placed in, the rotation speed is set to 300 rpm, and grinding is continued for 6 hours. FeOOH@BC particles are obtained by stopping for 5 minutes every 15 minutes of rotation. The preparation method of biochar is as follows: the biomass raw material is washed with pure water and dried at 65℃ for 72h. It is then filled into a quartz boat and placed in a high-temperature tube furnace. N2 is introduced and kept for 40min to remove the air in the furnace. The heating rate is set to 14℃ / min. After heating to 305℃, it is kept for 2h+5min. N2 is introduced as a protective gas throughout the preparation process. The biomass raw material is straw.

[0038] Example 13: This example provides a mobile skid-mounted, non-powered mine antimony-containing water inflow treatment method, based on the mobile skid-mounted, non-powered mine antimony-containing water inflow treatment system of Example 1, including the following steps: S1. Preparation: Prepare composite packing material and fill it into the adsorption filter tank 131. Place each chamber 1 side by side and connect them with connecting rod 2. Install limiting pins 5 on the two slots 4 at the beginning and end so that the whole system can be hoisted as a whole. S2. Lifting and Positioning: Locate the downstream position of the antimony-containing water inflow point in the mine to be treated. Lift the first and last lifting rings 42 and lift the system to this position. Then, align the water inlet hose 111 with the water inflow point. Extend the telescopic support leg 18 at the bottom of the buffer homogenization chamber 11 and insert it into the slope soil to keep the buffer homogenization chamber 11 fixed. Then, change the lifting position to the lifting rings 42 of the sedimentation chamber 12 and the clear water buffer chamber 14. At the same time, change the position of the limit pin 5 to the slot 4 of the sedimentation chamber 12 and the clear water buffer chamber 14. At this time, keep the system in the lifting state and lower it so that the slider 17 of the sedimentation chamber 12 slides in the slide rail 16 of the buffer homogenization chamber 11 until the sedimentation chamber 12 reaches the designated position. Then, extend the telescopic support leg 18 of the sedimentation chamber 12 and insert it into the slope soil to keep the sedimentation chamber 12 fixed. After that, complete the fixed positioning of the adsorption treatment chamber 13 and the clear water buffer chamber 14 in sequence according to the above method. Install the water guide hose 3 at each joint. S3. Continuous Water Treatment: Antimony-containing mine water enters the buffer homogenization chamber 11 through the inlet hose 111. After homogenization, it is guided to the sedimentation chamber 12 through the water guide hose 3 under gravity and siphon action. After sedimentation removes suspended solids, it is guided to the adsorption treatment chamber 13 through the water guide hose 3 under gravity and siphon action. After being adsorbed by each adsorption filter tank 131 in sequence, it is guided to the clear water buffer chamber 14 through the water guide hose 3 under gravity and siphon action, and then discharged through the siphon drain 141. The total hydraulic retention time is 0.5~2h, and the water quality inside the clear water buffer chamber 14 is sampled and monitored every 0.5h. The initial total hydraulic retention time is set to 1h. When the antimony concentration exceeds 0.015mg / L, the total hydraulic retention time is increased by 10%. When the antimony concentration is less than 0.005mg / L, the total hydraulic retention time is shortened by 10%.

[0039] Example 14: The difference between this example and Example 13 is that the water quality inside the clear water buffer tank 14 is sampled and monitored every 1 hour. The initial total hydraulic retention time is set to 1 hour. When the antimony concentration exceeds 0.015 mg / L, the total hydraulic retention time is increased by 20%. When the antimony concentration is less than 0.005 mg / L, the total hydraulic retention time is shortened by 20%.

[0040] Example 15: This example differs from Example 13 in that when the antimony concentration exceeds 0.015 mg / L, the total hydraulic residence time is increased by 15%, and when the antimony concentration is less than 0.005 mg / L, the total hydraulic residence time is shortened by 15%.

[0041] Experimental Example: To verify the performance of the composite filler prepared in this invention, namely the iron mineral-biochar composite material (BM-β-FeOOH / BC, where BM represents ball milling and BC represents biochar), and its compatibility with the entire system, we conducted the following experiments. For example... Figure 7 As shown, the specific surface area of ​​the original biochar is 2.671 m². 2 ·g -1 The specific surface area of ​​the composite material after ball milling and combining with FeOOH was significantly improved, and the specific surface area continued to increase (10.868~135.769 m²) with the increase of the ratio of FeOOH to BC (1:1~8:1). 2 ·g -1 The results indicate that ball milling increases the specific surface area of ​​biochar, and this increased surface area facilitates the exposure of functional groups and the binding of more contaminants. Pore volume exhibits a similar pattern; the pore volume of the ball-milled material gradually increases with the increasing ratio of FeOOH to BC. However, the change in biochar pore size is different; the pore size decreases with increasing FeOOH to BC ratio, indicating that FeOOH is embedded within the pores of BC and occupies some space.

[0042] Scanning electron microscopy results showed that the original BC surface was smooth with a multilayered and large porosity distribution. After ball milling with FeOOH, the surface of the biochar became rough, with obvious particulate matter adhering to the BC, some of which was embedded inside the BC. Furthermore, due to the interaction between the particles, some FeOOH aggregated together.

[0043] The composite packing material prepared by the method of this invention exhibits maximum adsorption capacities of 116.851 mg / g for Sb(III) and 109.357 mg / g for Sb(V), and demonstrates highly efficient and stable removal performance over a wide pH range (2-10) and under conditions where common anions coexist. The immobilization of Sb(III) shows stronger environmental adaptability. The optimal composite mass ratio of β-FeOOH to biochar is 3:1. Meanwhile, the synergistic removal mechanism of the material, characterized by "complexation-dominant and oxidation-assisted" action, was also revealed. The abundant Fe-OH functional groups on the material surface can form stable Fe-O-Sb intrasphere complexes with antimony through ligand exchange, achieving chemical fixation. At the same time, Fe(III) in β-FeOOH can oxidize some of the adsorbed Sb(III) to Sb(V) in situ, thereby reducing its toxicity.

[0044] Recycling Experiment: To investigate the reusability of the composite material, the composite material after adsorbing Sb was filtered, dried, and then desorbed in 0.1 mol / L HCl for 6 hours. After filtration and drying, it was re-immersed in the Sb-contaminated solution for 12 hours, and this cycle was repeated four times. The results showed that after four cycles, the removal rate of Sb(III) by BM-β-FeOOH / BC decreased slightly, but remained above 83.81%, while the removal rate of Sb(V) decreased to 59.12%. This indicates that BM-β-FeOOH / BC has certain regeneration adsorption performance and can be reused multiple times, but its adsorption and regeneration ability for Sb(III) is better than that for Sb(V).

[0045] The adsorption capacity of the composite material for Sb(III) and Sb(V) gradually decreased. On the one hand, with the increase of adsorption cycles, the biochar gradually aged, resulting in a reduction in its functional groups and pore size, thus weakening the adsorption of pollutants; on the other hand, H... + It may have some destructive ability on the internal structure of BM-β-FeOOH / BC, leading to a decrease in adsorption performance.

[0046] Dynamic column simulation experiment: The dynamic column experimental apparatus mainly consists of antimony-contaminated wastewater, a peristaltic pump, a peristaltic tube, an acrylic column filled with quartz sand and composite materials, and a collection tank. The antimony-contaminated wastewater was prepared with relevant reagents based on the Sb concentration and anion types and concentrations of an actual water sample from a mining area in Henan Province. The simulated column is 26 cm high and has an inner diameter of 2.8 cm. Both ends of the column are filled with a 3 cm thick layer of quartz sand with a particle size of 6-8 mesh as a buffer layer. Then, a 5 cm layer of quartz sand with a particle size of 120 mesh is filled at both ends to simulate an aquifer. The middle part is filled with a mixture of BM-β-FeOOH / BC and quartz sand as filter media (quartz sand:BM-β-FeOOH / BC = 30:1). All layers are compacted. A peristaltic pump is used to enter water from the bottom and exit water from the top of the dynamic column at a flow rate of 1 mL / min. Water samples are taken every 12 hours. During the experiment, the particle size of the intermediate layer quartz sand (24-40 mesh) and the flow rate of Sb-contaminated wastewater (0.5, 1, 2 mL / min) were adjusted as needed. When the influent flow rates were 0.5 mL / min, 1 mL / min, and 2 mL / min, the breakthrough times were 276 h, 114 h, and 40 h, respectively, and the depletion times were 540 h, 264 h, and 108 h, respectively. The simulated column treatment of Sb-contaminated wastewater exhibited three stages: complete removal, a decrease in removal rate, and removal saturation. This pattern is mainly due to the fact that in the early stage of the reaction, the surface of the BM-β-FeOOH / BC composite material filled in the simulated column has enough adsorption sites to completely adsorb Sb in the water, making Sb undetectable at the outlet. As the reaction time increases, the composite material filled in the simulated column continuously adsorbs pollutants, and the adsorption sites on its surface are gradually occupied, thus weakening the adsorption capacity. The composite material near the inlet reaches adsorption saturation first, and the height of the reaction wall with high adsorption capacity in the simulated column decreases, shortening the hydraulic residence time, i.e., the contact time between the pollutants and the material. Therefore, the removal rate of Sb by the simulated column gradually decreases until all the packing material reaches adsorption saturation.

[0047] As the influent flow rate increases, the Sb concentration in the effluent of the simulated column increases sequentially. The influent flow rate is negatively correlated with the Sb removal rate and the service life of the simulated column.

[0048] Dynamic column simulation experiments clearly showed that the influent flow rate is a key parameter for regulating the repair efficiency and service life of the filter tank, and the two are significantly negatively correlated. Under optimized conditions, the system can maintain effective operation for a long time, which provides important experimental evidence for the design and parameter control of actual PRB projects.

[0049] Taking the mine inflow water from an antimony mine in Henan Province as the research object, BM-β-FeOOH / BC was mixed with quartz sand at a mass ratio of 30:1 and used as filter media. Under an influent flow rate of 1.17 m / d, this system could achieve complete removal of Sb within a contact time of 10 min, with an effective operating time of up to 540 h and a cumulative treated wastewater volume of 16200 mL. The above research results indicate that the BM-β-FeOOH / BC composite material has good application prospects in actual antimony-contaminated groundwater purification projects.

Claims

1. A mobile skid-mounted, non-powered mine antimony-containing water treatment system, characterized in that, It includes several chambers (1) arranged side by side, namely, buffer homogenization chamber (11), sedimentation chamber (12), adsorption treatment chamber (13), and clear water buffer chamber (14). Each chamber (1) is arranged to slide up and down relative to each other, and each chamber (1) is fixedly connected by a connecting rod (2) located at the top. The buffer homogenization chamber (11) is equipped with a water inlet hose (111) at the front end, and each chamber (1) is connected to the other by a detachable water guide hose (3). The sedimentation chamber (12) is equipped with several inclined sedimentation components (121) for sedimentation to remove suspended solids. The adsorption treatment chamber (13) is equipped with several adsorption filter tanks (131) connected in series. Each adsorption filter tank (131) is equipped with composite packing material, which includes FeOOH@BC particles and inert support particles. The filling rate of the composite packing material in the adsorption filter tank (131) is 60-80%. The clear water buffer tank (14) is equipped with a siphon drainer (141). Each compartment (1) has an interface (15) for installing the water guide hose (3) at the bottom rear side and the top front side, and each water guide hose (3) is equipped with a valve.

2. The mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 1, characterized in that, In the composite packing, the mass ratio of FeOOH@BC particles to inert support particles is 1:25~35, the inert support particles are quartz sand, the inclined sedimentation component (121) includes 15~30 inclined plates or inclined tubes, and the adsorption filter (131) has 3~5 units.

3. A mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 2, characterized in that, The FeOOH@BC particles are prepared by adding biochar and β-FeOOH powder to a grinding container, wherein the mass ratio of β-FeOOH powder to biochar is 2~4:1, placing an agate ball in the container, setting the rotation speed to 300~400 rpm, and grinding continuously for 6~10 hours, stopping for 5~15 minutes every 15~30 minutes to obtain FeOOH@BC particles.

4. A mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 3, characterized in that, The preparation method of the biochar is as follows: the biomass raw material is washed with pure water and dried at 55~65℃ for 72h, filled into a quartz boat and placed in a high-temperature tube furnace, N2 is introduced and maintained for 20~40min to remove air from the furnace, the heating rate is set to 8~14℃ / min, and after heating to 300±5℃, it is maintained for 2h±5min. N2 is introduced as a protective gas throughout the preparation process. The biomass raw material is straw.

5. A mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 1, characterized in that, Each of the compartments (1) is connected on its outer side wall by a slide rail (16) and a slider (17). The slider (17) and the slide rail (16) are both T-shaped and matched. In two adjacent compartments (1), the slide rail (16) is located on the corresponding front compartment (1), and the slider (17) is located on the corresponding rear compartment (1). Each compartment (1) has a slot (4) at the top, and the connecting rod (2) passes through each slot (4).

6. A mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 5, characterized in that, Each of the slots (4) has a limiting hole (41) on its side wall, and each of the connecting rods (2) has a limiting groove (21) at the location of each limiting hole (41). The limiting groove (21) and the limiting hole (41) are connected by a limiting pin (5).

7. A mobile skid-mounted, non-powered mine antimony-containing water treatment system according to claim 5, characterized in that, Each slot (4) has a lifting ring (42) at the top, and each compartment (1) has several telescopic legs (18) at the bottom.

8. A method for treating antimony-containing inrush water in a mobile skid-mounted, non-powered mine shaft, based on the mobile skid-mounted, non-powered mine shaft antimony-containing inrush water treatment system described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Preparation: Prepare the composite filler and fill it into the adsorption filter tank (131). Place each of the chambers (1) side by side and connect them through the connecting rod (2) so that the whole system is hoisted as a whole. S2. Lifting and Positioning: Locate the downstream position of the antimony-containing water inflow point in the mine to be treated, lift and hoist the system to that position, and then align the water inlet hose (111) with the water inflow point. Fix the buffer homogenization chamber (11) in the slope soil to keep the buffer homogenization chamber (11) fixed. Then change the lifting position to the sedimentation chamber (12) and the clear water buffer chamber (14). At this time, keep the lifting position and lower it so that the sedimentation chamber (12) and the buffer homogenization chamber (11) slide relative to each other until the sedimentation chamber (12) reaches the designated position. Then fix the sedimentation chamber (12) in the slope soil to keep the sedimentation chamber (12) fixed. After that, follow the above method to complete the fixing and positioning of the adsorption treatment chamber (13) and the clear water buffer chamber (14) in sequence, and install the water guide hose (3) at each joint. S3. Continuous water treatment: Antimony-containing water from the mine enters the buffer homogenization chamber (11) through the inlet hose (111). After homogenization, it is guided to the sedimentation chamber (12) through the water guide hose (3) under the action of gravity and siphon. After sedimentation removes suspended solids, it is guided to the adsorption treatment chamber (13) through the water guide hose (3) under the action of gravity and siphon. After being adsorbed by each of the adsorption filter tanks (131), it is guided to the clear water buffer chamber (14) through the water guide hose (3) under the action of gravity and siphon, and then discharged through the siphon drainer (141).

9. A method for treating antimony-containing inrush water in a mobile skid-mounted, non-powered mine shaft according to claim 8, characterized in that, In S3, the total hydraulic retention time is 0.5~2h, and the water quality inside the clear water buffer tank (14) is sampled and monitored every 0.5~1h. The initial total hydraulic retention time is set to 1h. When the antimony mass concentration exceeds 0.015mg / L, the total hydraulic retention time is increased by 10~20%. When the antimony mass concentration is less than 0.005mg / L, the total hydraulic retention time is shortened by 10~20%.

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