A catalysis / filtration coupling device for treating phenolic wastewater
By integrating sludge biochar catalytic oxidation and microfiltration membrane in the same device and adopting a hierarchical pore structure, the problems of lengthy process and pollution in traditional processes are solved, achieving efficient and economical treatment of phenolic wastewater and extending the stable operation time of the system.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- HARBIN INSTITUTE OF TECHNOLOGY (SHENZHEN) (INSTITUTE OF SCIENCE AND TECHNOLOGY INNOVATION HARBIN INSTITUTE OF TECHNOLOGY SHENZHEN)
- Filing Date
- 2025-07-22
- Publication Date
- 2026-06-23
Smart Images
Figure CN224394740U_ABST
Abstract
Description
Technical Field
[0001] This utility model relates to an apparatus for treating phenolic wastewater. Background Technology
[0002] Phenolic wastewater mainly originates from industries such as petroleum refining, chemical processing, pharmaceuticals, and coking. It is characterized by the presence of toxic and harmful substances such as phenol, cresol, and chlorophenol, exhibiting high toxicity, recalcitrant degradation, and bioaccumulation, posing a serious threat to the ecological environment and human health. Traditional treatment methods include physical methods (such as adsorption and extraction), chemical methods (such as oxidation and flocculation), and biological methods (such as activated sludge and biofilms), but each has its limitations. Physical methods typically only transfer pollutants rather than completely degrade them. Chemical methods are costly and prone to secondary pollution. Biological methods have poor tolerance to high concentrations of phenols, limiting their treatment efficiency. In recent years, advanced oxidation technologies (such as Fenton oxidation and photocatalysis), membrane separation technologies, and bio-enhanced technologies have gradually become research hotspots, aiming to improve degradation efficiency and reduce treatment costs. Furthermore, with increasingly stringent environmental regulations, developing efficient, economical, and green phenolic wastewater treatment technologies has become an urgent industry need. However, traditional catalytic oxidation-membrane separation coupling processes suffer from three major technical bottlenecks: redundant unit length, catalyst loss, and membrane fouling. Utility Model Content
[0003] The present invention aims to solve the technical problems of existing catalytic oxidation-membrane separation coupling processes, such as redundant units, catalyst loss, and membrane fouling, and provides a catalytic / filtration coupling device for treating phenolic wastewater.
[0004] The catalytic / filtration coupling device for treating phenolic wastewater of this utility model consists of a bottom reactor 1, a stirrer 2, an upper reactor 3, a lower metal mesh support layer 4, a lower microfiltration membrane 5, a lower PP cotton layer 6, a sludge biochar layer 7, an upper PP cotton layer 8, an upper microfiltration membrane 9, an upper metal mesh support layer 10, and a motor 11.
[0005] The bottom reactor 1 is provided with a phenolic wastewater inlet 1-1 and a PDS raw material inlet 1-2 at the bottom. A motor 11 is also provided at the center of the bottom of the outer wall of the bottom reactor 1. A stirrer 2 is provided on the central axis of the inner cavity of the bottom reactor 1. The bottom of the stirrer 2 is connected to the power output end of the motor 11.
[0006] An upper reactor 3 is installed above the bottom reactor 1. The top of the bottom reactor 1 is connected to the bottom of the upper reactor 3. In the inner cavity of the upper reactor 3, from bottom to top, there are a lower metal mesh support layer 4, a lower microfiltration membrane 5, a lower PP cotton layer 6, a sludge biochar layer 7, an upper PP cotton layer 8, an upper microfiltration membrane 9, and an upper metal mesh support layer 10. An outlet 3-1 is installed at the top of the upper reactor 3.
[0007] The operation and working principle of the catalytic / filtration coupling device for treating phenolic wastewater of this utility model are as follows: The phenolic wastewater to be treated and the persulfate stock solution (PDS) are simultaneously pumped into the inner cavity of the bottom reactor 1 from the bottom through the phenolic wastewater inlet 1-1 and the PDS stock solution inlet 1-2, respectively. The stirrer 2 is driven by the motor 11 to rotate. After being stirred and mixed, the phenolic wastewater and persulfate stock solution enter the inner cavity of the upper reactor 3 from the top of the bottom reactor 1. They pass through the lower metal mesh support layer 4, the lower microfiltration membrane 5, and the lower PP cotton layer 6 in sequence and rise evenly. Then, they penetrate the sludge biochar layer 7. In the sludge biochar layer 7, the persulfate is activated by the active sites on the surface of the sludge biochar to generate various active oxides, which efficiently degrade the phenolic wastewater. Subsequently, the reaction mixture continues to pass through the upper PP cotton layer 8 and the upper microfiltration membrane 9 in sequence to complete particle interception and deep filtration. Finally, the purified water is discharged from the top outlet 3-1. Throughout the process, the reaction and separation are carried out continuously within the same device, achieving synergistic enhancement of catalytic oxidation and membrane separation.
[0008] The beneficial effects of this utility model are as follows:
[0009] I. This utility model is the first to couple catalytic oxidation of sludge biochar with microfiltration membrane in the same device, breaking through the traditional multi-stage series of "reaction tank + sedimentation tank + membrane tank", and significantly shortening the process and reducing dead volume and energy consumption with integrated design.
[0010] II. This utility model forms a bottom-up particle size barrier through a three-stage gradient interception structure of metal mesh-PP cotton-microfiltration membrane with graded pore size, which synergistically inhibits the loss of sludge biochar and membrane fouling, so that the sludge biochar maintains high activity during continuous operation. This ensures the quality of effluent while extending the stable operation cycle of the system, providing a new technical paradigm for the economical and efficient deep treatment of phenol-containing wastewater.
[0011] Third, the PP cotton layer and the pre-barrier of the microfiltration membrane effectively intercept micro-flocs and residual particles generated during the degradation process, significantly delaying the formation of the fouling layer on the membrane surface, thus achieving long-term stable flux without the need for backwashing or chemical cleaning.
[0012] The integrated design overcomes the shortcomings of traditional processes, such as complexity, high operating costs, and poor stability, and provides a feasible new path for efficient, economical, and continuous deep treatment of phenol-containing wastewater. Attached Figure Description
[0013] Figure 1 This is a schematic diagram of the catalytic / filtration coupling device for treating phenolic wastewater according to Specific Implementation Method 1. Detailed Implementation
[0014] Specific Implementation Method 1: This implementation method is a catalytic / filtration coupling device for treating phenolic wastewater, such as... Figure 1 As shown, it is specifically composed of a bottom reactor 1, a stirrer 2, an upper reactor 3, a lower metal mesh support layer 4, a lower microfiltration membrane 5, a lower PP cotton layer 6, a sludge biochar layer 7, an upper PP cotton layer 8, an upper microfiltration membrane 9, an upper metal mesh support layer 10, and a motor 11.
[0015] The bottom reactor 1 is provided with a phenolic wastewater inlet 1-1 and a PDS raw material inlet 1-2 at the bottom. A motor 11 is also provided at the center of the bottom of the outer wall of the bottom reactor 1. A stirrer 2 is provided on the central axis of the inner cavity of the bottom reactor 1. The bottom of the stirrer 2 is connected to the power output end of the motor 11.
[0016] An upper reactor 3 is installed above the bottom reactor 1. The top of the bottom reactor 1 is connected to the bottom of the upper reactor 3. In the inner cavity of the upper reactor 3, from bottom to top, there are a lower metal mesh support layer 4, a lower microfiltration membrane 5, a lower PP cotton layer 6, a sludge biochar layer 7, an upper PP cotton layer 8, an upper microfiltration membrane 9, and an upper metal mesh support layer 10. An outlet 3-1 is installed at the top of the upper reactor 3.
[0017] The method of use and working principle of the catalytic / filtration coupling device for treating phenolic wastewater in this embodiment is as follows: The phenolic wastewater to be treated and the persulfate stock solution (PDS, as an oxidant) are simultaneously pumped from the bottom into the inner cavity of the bottom reactor 1 through the phenolic wastewater inlet 1-1 and the PDS stock solution inlet 1-2, respectively. The stirrer 2 is driven by the motor 11 to rotate. After being stirred and mixed, the phenolic wastewater and persulfate stock solution enter the inner cavity of the upper reactor 3 from the top of the bottom reactor 1. They pass through the lower metal mesh support layer 4, the lower microfiltration membrane 5, and the lower PP cotton layer 6 in sequence and rise evenly. Then, they penetrate the sludge biochar layer 7 (activator). In the sludge biochar layer 7, the persulfate is activated by the active sites on the surface of the sludge biochar to generate various active oxides, which efficiently degrade the phenolic wastewater. Subsequently, the reaction mixture continues to pass through the upper PP cotton layer 8 and the upper microfiltration membrane 9 in sequence to complete particle interception and deep filtration. Finally, the purified water is discharged from the top outlet 3-1. Throughout the process, the reaction and separation are carried out continuously within the same device, achieving synergistic enhancement of catalytic oxidation and membrane separation.
[0018] The beneficial effects of this embodiment are as follows:
[0019] I. This embodiment is the first to couple catalytic oxidation of sludge biochar with microfiltration membrane in the same device, breaking through the traditional multi-stage series of "reaction tank + sedimentation tank + membrane tank", and significantly shortening the process and reducing dead volume and energy consumption with integrated design.
[0020] II. This embodiment uses a three-level gradient interception structure of metal mesh-PP cotton-microfiltration membrane with graded pore size to form a bottom-up particle size barrier, which synergistically inhibits the loss of sludge biochar and membrane fouling, so that the sludge biochar maintains high activity during continuous operation. This ensures the quality of effluent while extending the stable operation cycle of the system, providing a new technical paradigm for the economical and efficient deep treatment of phenol-containing wastewater.
[0021] Third, the PP cotton layer and the pre-barrier of the microfiltration membrane effectively intercept micro-flocs and residual particles generated during the degradation process, significantly delaying the formation of the fouling layer on the membrane surface, thus achieving long-term stable flux without the need for backwashing or chemical cleaning.
[0022] The integrated design overcomes the shortcomings of traditional processes, such as complexity, high operating costs, and poor stability, and provides a feasible new path for efficient, economical, and continuous deep treatment of phenol-containing wastewater.
[0023] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the pore size of the lower microfiltration membrane 5 is 0.45 μm. Everything else is the same as in Specific Implementation Method One.
[0024] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 2 in that the pore size of the lower PP cotton layer 6 is 1μm. Everything else is the same as in Specific Implementation Method 2.
[0025] Specific Implementation Method Four: This implementation method differs from Specific Implementation Method Three in that the pore size of the upper PP cotton layer 8 is 1μm. Everything else is the same as in Specific Implementation Method Three.
[0026] Specific Implementation Method Five: This implementation method differs from Specific Implementation Method Four in that the pore size of the upper microfiltration membrane 9 is 0.22 μm. Everything else is the same as in Specific Implementation Method Four.
[0027] Specific Implementation Method Six: This implementation method differs from Specific Implementation Method Five in that the thickness of both the lower PP cotton layer 6 and the upper PP cotton layer 8 is 6cm. Everything else is the same as in Specific Implementation Method Five.
[0028] Experiment 1: The apparatus in Specific Implementation Method 6 was used to treat phenol wastewater. The specific process parameters are as follows: the concentration of PDS in the mixed liquid in the bottom reactor 1 is 4 mM; the rotation speed of the stirrer 2 is 50 rpm; the inlet flow rate of the phenol wastewater inlet 1-1 is 20 mL / min; the specific inlet and outlet water quality are shown in Table 1.
[0029] Table 1
[0030] Water ingress Out of water pH 3～6 3～6 Phenol concentration 5mg / L 0~0.5mg / L COD 15mg / L 9.6 mg / L
[0031] The preparation method of sludge biochar layer 7 in this experiment is an existing method, specifically as follows: First, the raw sludge is exposed to sunlight to reduce its moisture content, then dried in an oven at 105℃ until it reaches a fixed weight. After crushing, it is screened using a 100-mesh screen. Subsequently, the sludge is placed in a tubular furnace, and nitrogen gas is introduced into the equipment at a flow rate of 80 mL / min to keep the inside of the tubular furnace in an anaerobic state. The pyrolysis temperature is reached at a temperature gradient of 5℃ / min, and the pyrolysis temperature is 1000℃. The corresponding temperature is maintained for pyrolysis for 120 min. Then, the product is thoroughly soaked and stirred in anhydrous ethanol solution for 2 h, followed by purification and soaking in ultrapure water for 30 min, and then vacuum filtered and dried to obtain sludge biochar.
Claims
1. A catalytic / filtration coupling device for treating phenolic wastewater, characterized in that... The device consists of a bottom reactor (1), a stirrer (2), an upper reactor (3), a lower metal mesh support layer (4), a lower microfiltration membrane (5), a lower PP cotton layer (6), a sludge biochar layer (7), an upper PP cotton layer (8), an upper microfiltration membrane (9), an upper metal mesh support layer (10), and a motor (11). The bottom reactor (1) is provided with a phenolic wastewater inlet (1-1) and a PDS raw liquid inlet (1-2) at the bottom. A motor (11) is also provided at the center of the bottom of the outer wall of the bottom reactor (1). A stirrer (2) is provided on the central axis of the inner cavity of the bottom reactor (1). The bottom of the stirrer (2) is connected to the power output end of the motor (11). An upper reactor (3) is set above the bottom reactor (1). The top of the bottom reactor (1) is connected to the bottom of the upper reactor (3). In the inner cavity of the upper reactor (3), from bottom to top, there are a lower metal mesh support layer (4), a lower microfiltration membrane (5), a lower PP cotton layer (6), a sludge biochar layer (7), an upper PP cotton layer (8), an upper microfiltration membrane (9), and an upper metal mesh support layer (10). An outlet (3-1) is set at the top of the upper reactor (3).
2. The catalytic / filtration coupling device for treating phenolic wastewater according to claim 1, characterized in that... The pore size of the lower microfiltration membrane (5) is 0.45 μm.
3. The catalytic / filtration coupling device for treating phenolic wastewater according to claim 1, characterized in that... The pore size of the lower PP cotton layer (6) is 1μm.
4. The catalytic / filtration coupling device for treating phenolic wastewater according to claim 1, characterized in that... The pore size of the upper PP cotton layer (8) is 1μm.
5. The catalytic / filtration coupling device for treating phenolic wastewater according to claim 1, characterized in that... The pore size of the microfiltration membrane (9) is 0.22 μm.
6. The catalytic / filtration coupling device for treating phenolic wastewater according to claim 1, characterized in that... The thickness of both the lower PP cotton layer (6) and the upper PP cotton layer (8) is 6cm.