Coal chemical wastewater treatment system and method integrating hydrogen production by cyclone and fenton degradation of pollutants

Abstract

The application provides a coal chemical alcohol-containing wastewater treatment system and method integrating hydrogen production by cyclone and self-Fenton pollutant degradation, and relates to the field of industrial wastewater treatment. The system comprises: a pretreatment unit for receiving a methanol-rich solution and removing acid gas; a shunt regeneration unit for shunting the liquid phase output by a heat regeneration tower, one way being sent to a cyclone oscillation hydrogen generator and the other way being sent to a cyclone gas-liquid separator to recover methanol-poor solution; a core treatment unit adopting a vertical inclined cyclone oscillation hydrogen generator, which generates highly active hydroxyl radicals in situ under extreme conditions generated by cyclone and directly uses the hydroxyl radicals for pollutant oxidative degradation, and simultaneously couples a hydrogen production process to realize the synergistic effect of water purification and energy recovery; and a product separation unit for recovering generated hydrogen and clear liquid after solid-liquid separation respectively. The application realizes wastewater purification, green hydrogen production and catalyst recovery simultaneously in the same process through highly integrated design, and has excellent environmental benefits and economy.

Description

Technical Field

[0001] This invention relates to the field of industrial wastewater treatment, and in particular to a coal chemical alcohol-containing wastewater treatment system and method that integrates cyclone hydrogen production and self-degradation of Fenton pollutants. Background Technology

[0002] Coal chemical processes involving alcohols are widely used in the production of acidic gases (such as syngas, natural gas, etc.) in industrial gases. , The process involves the removal of methanol. Using methanol as the absorbent, this process generates a large amount of methanol-rich wastewater (or waste methanol-water solution) during operation. This wastewater has a complex composition, typically containing incompletely recovered methanol and dissolved methanol. , It also contains small amounts of other organic sulfides and organic matter, characterized by high chemical oxygen demand (COD), a certain degree of toxicity, and difficulty in direct biochemical treatment. Improper handling will not only cause serious environmental pollution, but also mean the waste of valuable materials (such as methanol and potential energy).

[0003] Currently, the main methods for treating alcohol-containing wastewater from coal chemical industries are as follows: Incineration uses wastewater as fuel in incinerators, which can completely decompose organic matter, but it is extremely energy-intensive and does not utilize the chemical value of the wastewater, while potentially generating secondary pollutants (such as NOx). Biological treatment uses anaerobic or aerobic biological processes. However, the high concentrations of methanol and sulfides in the wastewater have strong inhibitory and toxic effects on microorganisms, requiring large amounts of dilution water and complex pretreatment, resulting in large-scale treatment facilities, slow start-up, unstable operation, and no energy recovery. Advanced oxidation processes utilize strong oxidants to degrade organic matter. This method typically has high operating costs, may produce chemical sludge, and only focuses on the destruction of pollutants, failing to realize the resource utilization of the chemical energy contained in the organic matter in the wastewater.

[0004] Hydrogen, as a clean energy carrier and an important chemical raw material, has attracted widespread attention for its green production technology. Traditional methanol reforming hydrogen production technology requires high-purity methanol and a dedicated reactor, resulting in a complex system and high energy consumption. In recent years, research has explored the use of methanol-containing wastewater for catalytic reforming hydrogen production, which can both purify wastewater and produce hydrogen, representing an attractive resource utilization pathway. However, existing technologies of this kind typically have the following limitations: low reaction efficiency, requiring a large amount of external heat; catalysts are easily poisoned or deactivated by impurities in the wastewater (such as sulfides); separation and recovery of the catalyst and water after the reaction are difficult, easily leading to catalyst loss and secondary pollution; the process flow is often independent of the upstream methanol washing process, failing to achieve synergistic optimization of materials and energy, resulting in low system integration.

[0005] On the other hand, advanced oxidation processes are an effective means of treating recalcitrant organic wastewater. Among them, the Fenton oxidation process has attracted widespread attention due to its ability to generate highly oxidizing hydroxyl radicals, resulting in thorough oxidation of organic matter and a rapid reaction rate. Traditional Fenton processes require the external addition of ferrous salts and hydrogen peroxide, which is not only costly but also has strict pH requirements (typically 2.5-3.5), and produces a large amount of iron-containing sludge after treatment, increasing the burden on subsequent treatment. To address these issues, researchers have developed "self-Fenton" technology. Its core concept is to utilize the components of the wastewater itself or substances generated in situ to construct the Fenton reaction system, thereby reducing or replacing the addition of external chemicals.

[0006] In summary, existing technologies for treating alcohol-containing wastewater from coal chemical processes generally suffer from high treatment costs, lack of resource recovery, and potential secondary pollution. Research into using this wastewater for hydrogen production faces challenges such as system independence, limited efficiency, difficulty in catalyst separation and recovery, and loose coupling with upstream processes. Therefore, developing a system that can be deeply integrated with coal chemical alcohol-containing processes to simultaneously achieve efficient wastewater purification, Fenton pollutant degradation, green hydrogen production, and convenient catalyst recovery has significant industrial application value and environmental implications. Summary of the Invention

[0007] In view of this, the purpose of this invention is to overcome the shortcomings of the prior art and provide a coal chemical alcohol wastewater treatment system and method that integrates cyclone hydrogen production and self-Fenton pollutant degradation, so as to achieve the simultaneous completion of catalytic degradation of pollutants, green production of hydrogen and separation and recovery of catalysts in the same highly integrated process, thereby achieving the dual goals of pollutant treatment and resource utilization, and improving the economy and environmental protection of the entire process.

[0008] This invention provides the following technical solution: In a first aspect, embodiments of this application provide a coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-degradation of Fenton pollutants, comprising: The pretreatment and acid gas removal unit includes a flash tank, a reabsorption tower and a thermal regeneration tower connected in sequence along the material flow direction. The flash tank is provided with an inlet for receiving a methanol-rich solution from the coal chemical alcohol-containing unit, and the thermal regeneration tower is provided with a liquid phase outlet. The diversion and regeneration unit includes a diversion pipeline and a cyclone gas-liquid separator. The inlet of the diversion pipeline is connected to the liquid phase outlet of the thermal regeneration tower. The outlet of the diversion pipeline is divided into a first branch and a second branch. A cyclone oscillating hydrogen generator is provided on the first branch. The second branch is connected to the feed inlet of the cyclone gas-liquid separator. The cyclone gas-liquid separator is provided with a regenerated liquid outlet for outputting lean methanol. A cyclone oscillation hydrogen production and self-Fenton pollutant degradation unit includes a cyclone oscillation hydrogen generator. The cyclone oscillation hydrogen generator includes a vertical container, a cyclone core tube, and a three-layer cylinder. The three-layer cylinder divides the inner cavity of the vertical container from the inside to the outside into an overflow cavity, an inlet cavity, and a bottom flow cavity. The cyclone core tube is inclinedly disposed in the inlet cavity. A tangential inlet is provided on the side wall of the cyclone core tube. The tangential inlet is connected to the first branch through an inlet pipe located below the inlet cavity. The top end of the cyclone core tube is connected to the overflow cavity, and the bottom end is connected to the bottom flow cavity. The product separation and resource recovery unit includes a hydrogen collection device and a settling tank. The inlet of the hydrogen collection device is connected to the overflow port at the top of the overflow chamber through a gas pipeline, and the liquid inlet of the settling tank is connected to the bottom outlet at the bottom of the underflow chamber through a liquid pipeline.

[0009] In some embodiments of the first aspect, the inner diameter of the swirl core tube is 10 mm to 50 mm, and the material flow velocity in the inlet tube is controlled between 1.5 m / s and 3 m / s, so that the fluid in the swirl field generates shear stress on the piezoelectric catalyst, inducing the catalyst to deform.

[0010] In some embodiments of the first aspect, the piezoelectric catalyst is sheet-like Mo. Mo-based composite catalyst, the sheet-like Mo When the sheet planes of the composite catalyst move with the fluid, they are not perpendicular to the streamline direction in the swirling flow field. Under the shearing action of the fluid, the catalyst induces lattice distortion and generates a polarized electric field.

[0011] In some embodiments of the first aspect, the three-layer cylinder includes an inner cylinder, a middle cylinder, and an outer cylinder that are coaxially nested. The internal space of the inner cylinder forms the overflow cavity, the annular space between the inner cylinder and the middle cylinder forms the inlet cavity, and the annular space between the middle cylinder and the outer cylinder forms the underflow cavity. The swirl core tube passes through the inlet cavity and is fixed to the inner cylinder and the middle cylinder by a flange connector.

[0012] In some embodiments of the first aspect, the swirling oscillating hydrogen generator is a multi-stage parallel structure, with the first branch inlet of each stage of the swirling oscillating hydrogen generator connected to the branch pipeline, the overflow outlet of each stage of the swirling oscillating hydrogen generator connected to the hydrogen collection device, and the underflow outlet of each stage of the swirling oscillating hydrogen generator connected to the settling tank.

[0013] In some embodiments of the first aspect, the bottom of the settling tank is provided with a catalyst outlet, which is connected to the inlet pipe of the cyclone oscillating hydrogen generator through a return pipeline with a delivery pump to form a catalyst circulation loop; the top or upper sidewall of the settling tank is provided with a purified water outlet.

[0014] In some embodiments of the first aspect, the hydrogen collection device includes a cyclone gas-liquid separator, a gas dryer, and a hydrogen storage tank connected in sequence, wherein the inlet of the cyclone gas-liquid separator is connected to the overflow port, and the liquid phase outlet of the cyclone gas-liquid separator is returned to the settling tank or discharged as purified water.

[0015] In some embodiments of the first aspect, the cyclone core tube has an angle of 110° to 120° with respect to the vertical direction.

[0016] Secondly, this application also provides a method for treating coal chemical alcohol-containing wastewater that integrates cyclone hydrogen production and self-degradation of Fenton pollutants, applied to the system described in any one of the above embodiments, comprising the following steps: S100: The methanol-rich solution from the coal chemical alcohol-containing unit is fed into a flash tank for flash evaporation, and then sequentially passed into a reabsorption tower and a thermal regeneration tower to remove methanol. and A deacidified methanol-rich solution was obtained; S200: The deacidified methanol-rich solution is split, with one part sent to a cyclone gas-liquid separator to be regenerated into lean methanol and returned to the coal chemical alcohol-containing unit, and the other part sent as a treatment liquid to a cyclone oscillating hydrogen generator. S300: Add flake Mo to the treatment solution The piezoelectric catalyst is fed tangentially from the bottom into the cyclone core tube at a flow rate of 1.5 m / s to 3 m / s. The fluid shear force causes the catalyst to generate a piezoelectric effect, and a redox reaction occurs on the catalyst surface, simultaneously achieving hydrogen production and self-Fenton degradation of organic pollutants. The residence time of the mixture in the cyclone core tube is controlled to be 5 s to 20 s. S400: Utilizing the negative pressure environment at the center of the swirling flow field, the generated hydrogen gas migrates towards the axis and exits from the overflow port, and is collected after gas-liquid separation; the catalyst and the liquid after reaction move towards the side wall under the action of centrifugal force and are discharged from the bottom outlet. S500: The mixture discharged from the underflow outlet is sent to the settling tank for solid-liquid separation. The recovered catalyst is returned to the cyclone oscillator for recycling after hydrothermal regeneration.

[0017] In some embodiments of the second aspect, in S300, the self-Fenton degradation process utilizes hydroxyl radicals generated in situ by piezoelectric catalytic water oxidation reaction to degrade organic matter. No additional iron salt catalysts or exogenous hydrogen peroxide are added during the reaction process, and the pH value of the reaction system is the original pH value of the methanol-rich solution after deacidification.

[0018] The embodiments of the present invention have the following advantages: The coal chemical alcohol-containing wastewater treatment system provided by this invention integrates cyclone hydrogen production and self-Fenton pollutant degradation. By directly using the methanol-rich wastewater generated from coal chemical alcohol production as raw material for cyclone hydrogen production, the system simultaneously achieves green hydrogen production (resource utilization) and efficient degradation (harmlessness) of organic pollutants, thus achieving the dual goals of treatment and utilization.

[0019] This invention utilizes substances or reaction processes generated in situ in wastewater to construct a self-Fenton oxidation system, requiring little or no external chemicals, significantly reducing operating costs and the amount of chemical sludge generated, and avoiding secondary pollution.

[0020] This invention employs a swirling oscillating hydrogen generator. Its swirling structure enhances mass and heat transfer, improves hydrogen production efficiency, and reduces the need for external heating. Furthermore, it utilizes centrifugal force to achieve efficient in-situ separation of the catalyst and the post-reaction liquid (the catalyst is retained in the swirling core tube or underflow, and purified water is discharged from the overflow port), avoiding catalyst loss, simplifying the recovery process, and solving the problem of difficult separation in traditional fixed-bed or slurry-bed reactors.

[0021] This invention directly connects the wastewater treatment system with the flash tank, reabsorption tower, thermal regeneration tower, and cyclone gas-liquid separator of the coal chemical alcohol-containing unit, forming an integrated process. For example, the methanol-rich solution drawn from the thermal regeneration tower is split, with one part used for hydrogen production and the other part entering the cyclone gas-liquid separator to regenerate lean methanol and return to the main system, realizing the recycling of methanol solvent. Simultaneously, the hydrogen production reaction can fully utilize the waste heat from the wastewater and may reuse the produced hydrogen or reaction heat upstream, significantly improving overall energy efficiency and material utilization.

[0022] Through a pretreatment and acid gas removal unit (flash evaporation, reabsorption, and thermal regeneration), gases that could easily poison the catalyst in the wastewater are first removed. The presence of sulfides makes the wastewater entering the cyclone hydrogen generator more catalyst-friendly, extending catalyst life. Simultaneously, the cyclone oscillation flow pattern inhibits coking or contamination on the catalyst surface, maintaining high reforming reaction activity.

[0023] The system's split pipeline design allows for flexible allocation of wastewater entering the hydrogen production unit and methanol recovery unit, which can be adjusted according to actual hydrogen demand or wastewater treatment load. The vertical inclined swirl oscillator hydrogen generator has a compact structure, no moving parts, is easy to scale up and industrially apply, and the tilt angle optimizes solid-liquid separation efficiency.

[0024] In summary, this invention overcomes the common defects of existing technologies, such as high processing costs, resource waste, secondary pollution, difficulty in catalyst reuse, and low system integration, by integrating coal chemical alcohol production, self-Fenton oxidation, cyclone-enhanced hydrogen production, and catalyst separation and recovery into a closed-loop process. It achieves integrated synergy of wastewater purification, hydrogen production, methanol recovery, and catalyst recycling, resulting in significant economic and environmental benefits.

[0025] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a schematic diagram of a coal chemical alcohol-containing wastewater treatment system that integrates cyclone hydrogen production and self-Fenton pollutant degradation in one embodiment of the present invention.

[0028] Figure 2 This is a schematic diagram of the structure of a swirling oscillation hydrogen generator according to one embodiment of the present invention.

[0029] Figure 3 This is a schematic diagram of the deformation of a molybdenum disulfide-based catalyst under shear force in one embodiment of the present invention.

[0030] Figure 4 This is a flowchart illustrating the principle of a coal chemical alcohol-containing wastewater treatment method integrating cyclone hydrogen production and self-Fenton pollutant degradation in one embodiment of the present invention.

[0031] Explanation of key component symbols: 1-Flash tank; 2-Reabsorption tower; 3-Thermal regeneration tower; 4-Coal chemical alcohol unit; 5-Swirl gas-liquid separator; 6-Swirl oscillating hydrogen generator; 7-Hydrogen storage tank; 8-Settling tank. Detailed Implementation

[0032] Embodiments of the present invention are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0033] It should be noted that when an element is said to be "fixed" to another element, it can be directly on the other element or there may be an intervening element. When an element is said to be "connected" to another element, it can be directly connected to the other element or there may be an intervening element. Conversely, when an element is said to be "directly" on another element, there is no intervening element. The terms "vertical," "horizontal," "left," "right," and similar expressions used in this document are for illustrative purposes only.

[0034] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0035] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the template description is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0037] like Figures 1 to 3 As shown, in order to solve the above-mentioned technical problems, this application provides a coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-Fenton pollutant degradation, comprising: The pretreatment and acid gas removal unit includes a flash tank 1, a reabsorption tower 2 and a thermal regeneration tower 3 connected in sequence along the material flow direction. The flash tank 1 is provided with an inlet for receiving a methanol-rich solution from the coal chemical alcohol-containing unit, and the thermal regeneration tower 3 is provided with a liquid phase outlet. The diversion and regeneration unit includes a diversion pipeline and a cyclone gas-liquid separator 5. The inlet of the diversion pipeline is connected to the liquid phase outlet of the thermal regeneration tower 3. The outlet of the diversion pipeline is divided into a first branch and a second branch. A cyclone oscillating hydrogen generator 6 is provided on the first branch. The second branch is connected to the feed inlet of the cyclone gas-liquid separator 5. The cyclone gas-liquid separator 5 is provided with a regenerated liquid outlet for outputting lean methanol. A cyclone oscillation hydrogen production and self-Fenton pollutant degradation unit includes a cyclone oscillation hydrogen generator. The cyclone oscillation hydrogen generator includes a vertical container, a cyclone core tube, and a three-layer cylinder. The three-layer cylinder divides the inner cavity of the vertical container from the inside to the outside into an overflow cavity, an inlet cavity, and a bottom flow cavity. The cyclone core tube is inclinedly disposed in the inlet cavity. A tangential inlet is provided on the side wall of the cyclone core tube. The tangential inlet is connected to the first branch through an inlet pipe located below the inlet cavity. The top end of the cyclone core tube is connected to the overflow cavity, and the bottom end is connected to the bottom flow cavity. The product separation and resource recovery unit includes a hydrogen collection device and a settling tank 8. The inlet of the hydrogen collection device is connected to the overflow port at the top of the overflow chamber through a gas pipeline, and the liquid inlet of the settling tank 8 is connected to the underflow port at the bottom of the underflow chamber through a liquid pipeline.

[0038] In these embodiments, regarding the pretreatment and acid gas removal unit: Flash tank 1 is designed for vertical installation and is equipped with a heating jacket to maintain the internal temperature between 30-40°C, promoting the dissolution of gases. The release of methanol. Flash tank 1 is used to receive and pre-treat the methanol-rich solution from the methanol-containing unit 4 of the coal chemical plant. Methanol-containing unit 4 of the coal chemical plant is used to receive the methanol-lean solution.

[0039] The reabsorption tower 2 adopts a packed tower structure and uses circulating water cooling to reduce the tower top temperature to 20-25°C, thereby improving the absorption efficiency.

[0040] The thermal regeneration tower 3 uses indirect steam heating to control the bottom temperature at 70-80°C, so that the methanol in the methanol-rich solution can be regenerated and recovered.

[0041] Regarding the shunt and regeneration unit: The cyclone gas-liquid separator 5 adopts a multi-stage distillation column form, with the top temperature set at 65°C and the bottom temperature at 100°C, using different boiling points to separate methanol and water.

[0042] The swirl oscillation hydrogen generator 6 has a built-in micro swirl generator. By adjusting the angle and size of the tangential inlet, the velocity distribution when the methanol solution enters is optimized, thereby enhancing the swirl effect and improving the hydrogen production efficiency.

[0043] Regarding the swirl-oscillation hydrogen production and self-Fenton pollutant degradation unit: Cyclone Oscillating Hydrogen Generator: The three-layer cylinder design creates a strong swirling motion of material within the inlet chamber, promoting the decomposition of methanol to generate hydrogen and other byproducts. The overflow chamber is used to collect light gases (mainly hydrogen), while the underflow chamber is responsible for discharging heavy substances.

[0044] For example, the cyclone oscillation hydrogen generator is a vertical, inclined single-tube bottom-feed liquid-solid micro cyclone hydrogen generator.

[0045] For example, the tilt angle of the cyclone core tube is set to 15°, and the diameter of the tangential inlet on the side wall is 2cm to ensure sufficient flow velocity to generate an effective cyclone effect.

[0046] Regarding the product separation and resource recovery unit: The hydrogen collection device is equipped with a condenser and a dryer to first purify the collected mixed gas, removing moisture and other impurities, and then compress and store it.

[0047] Settling tank 8 is used to settle solid particles flowing out of the underflow chamber and is cleaned regularly to prevent blockage.

[0048] Based on the above basic configuration, if it is necessary to treat methanol wastewater with a higher concentration, the operating pressure of the thermal regeneration tower 3 can be increased, and the circulating water volume in the reabsorption tower 2 can be increased to meet the higher load requirements.

[0049] Pretreatment and Acid Gas Removal Unit: This unit receives and pre-treats the methanol-rich solution from the methanol-containing unit 4 in the coal chemical industry. This unit sequentially includes a flash tank 1, a reabsorption tower 2, and a thermal regeneration tower 3. The methanol-rich solution first enters the flash tank 1 for flash evaporation, releasing some dissolved gases. Subsequently, the liquid is sequentially passed through the reabsorption tower 2 and the thermal regeneration tower 3, where desorption and regeneration processes remove impurities from the wastewater. and Acidic gases are selectively and completely removed and discharged from the system in gaseous form, thereby avoiding their poisoning of downstream hydrogen production catalysts.

[0050] The methanol diversion and regeneration unit: After deacidification, the methanol-rich solution is diverted into two streams. The first stream is directed to the core cyclone oscillating hydrogen generator 6. The second stream enters the cyclone gas-liquid separator 5, where methanol and water are separated through distillation. The regenerated lean methanol solution can be returned to the coal chemical alcohol-containing unit 4 for recycling, achieving closed-loop regeneration and conservation of the absorbent.

[0051] Cyclone Oscillating Hydrogen Production and Self-Fenton Pollutant Degradation Unit: The core equipment of this unit is the cyclone oscillating hydrogen generator 6. A first-stream methanol-rich solution from the split unit is injected from the bottom of this cyclone oscillating hydrogen generator 6. A specific piezoelectric solid catalyst (such as Mo) is used. The catalyst is introduced into the hydrocyclone hydrogen generator along with the methanol-rich solution. The catalyst and wastewater are mixed by shear oscillation in the swirling field of the micro-cyclone, which excites the piezoelectric effect. This greatly enhances the mass transfer and mixing process between the liquid, solid, and gas phases, promoting the efficient conversion of the methanol-rich solution in the wastewater into hydrogen, while simultaneously achieving deep degradation of organic pollutants by Fenton.

[0052] Product separation and resource recovery unit: Under the enhanced negative pressure at the center of the flow field within the hydrocyclone, hydrogen gas is rapidly released from the gas overflow port at the top of the hydrocyclone oscillating hydrogen generator 6 and enters the hydrogen storage tank 7. After further purification, it can be utilized as a clean energy source or chemical feedstock. Biochemically treatable wastewater carrying catalyst particles is discharged from the bottom of the hydrocyclone oscillating hydrogen generator 6 into the settling tank 8. In the settling tank 8, using gravity settling, the solid catalyst particles are efficiently separated from the liquid phase and deposited for recovery. After simple hydrothermal regeneration, they are returned to the hydrogen generator for recycling, avoiding catalyst loss and secondary pollution. The separated liquid phase has a significantly reduced COD value, meeting reuse standards or meeting biochemical wastewater treatment requirements.

[0053] Through the organic connection and synergistic operation of the above units, this system realizes the integrated treatment and resource recovery of the entire process from pollutant-rich methanol wastewater to regenerated lean methanol, biochemical wastewater, hydrogen products and recovered catalysts.

[0054] In some embodiments, the inner diameter of the swirl core tube is 10 mm to 50 mm, and the material flow velocity in the inlet tube is controlled between 1.5 m / s and 3 m / s, so that the fluid in the swirl field generates shear stress on the piezoelectric catalyst, inducing the catalyst to deform.

[0055] In these embodiments, the specific structure and operating parameters of the swirling oscillating hydrogen generator 6 are optimized to maximize the activity of the piezoelectric catalyst and enhance multiphase mass transfer.

[0056] For example, the swirl core tube is made of stainless steel or corrosion-resistant ceramic material, with an inner diameter of 10 mm to 50 mm, preferably 25 mm. This size range ensures sufficient flow cross-sectional area to avoid clogging while creating a high-intensity swirling field within a limited space.

[0057] The first stream of methanol-rich solution from the splitting unit is injected tangentially from the bottom of the cyclone core via the inlet pipe. The material flow velocity in the inlet pipe is controlled between 1.5 m / s and 3.0 m / s by adjusting the pumping system; a velocity of 1.5 m / s, 2.2 m / s, or 3.0 m / s can be selected. Within this velocity range, the fluid forms a high-speed rotating flow near the inner wall of the cyclone core, which affects the piezoelectric solid catalyst particles (such as Mo) suspended in the liquid phase. , or BaTi Significant shear stress is applied to the matrix composite material.

[0058] The shear stress acts on the catalyst surface, causing deformation and inducing lattice distortion, thereby generating a built-in electric field. Driven by periodic mechanical stress, a local potential difference is generated inside the catalyst, promoting the cracking of water molecules to generate hydroxyl radicals (achieving self-Fenton oxidation), which can realize hydrogen evolution and COD removal.

[0059] In some embodiments, the piezoelectric catalyst is sheet-like Mo. Mo-based composite catalyst, the sheet-like Mo When the planar sheets of the composite catalyst move with the fluid, they are not perpendicular to the streamline direction in the swirling flow field. The catalyst deforms under the shearing action of the fluid to generate a piezoelectric potential.

[0060] In these embodiments, the piezoelectric catalyst used in the swirl oscillating hydrogen generator 6 is plate-shaped Mo. A two-dimensional layered catalyst. This catalyst is synthesized via a hydrothermal method and exhibits a typical two-dimensional layered structure.

[0061] When the sheet-like catalyst enters the cyclone core along with the methanol-rich wastewater, it moves with the fluid in the high-speed swirling flow field. Due to the strong velocity gradient and shear streamlines within the swirling flow field, the sheet-like planes of the catalyst spontaneously adjust their orientation under the drag force of the fluid, so that they are not perpendicular to the local streamline direction, but rather inclined or parallel (typically with an included angle of 15°-75°). This non-perpendicular orientation significantly reduces fluid resistance and prolongs the residence time of the catalyst in the high-shear region.

[0062] More importantly, under continuous fluid shearing, flexible Mo... The lamellar layers undergo periodic bending or twisting deformation. This is due to Mo... The lack of centrosymmetry in the crystal structure means that such mechanical deformation disrupts the lattice charge balance, inducing a piezoelectric potential difference across the lamellae. This in-situ generated electric field can: Promote Molecules undergo polarization and cleave on the catalyst surface to generate hydroxyl radicals, without the need for external additives. or This achieves self-Fenton oxidation.

[0063] The above results indicate that by controlling the coupling behavior between the catalyst morphology (plate-like) and the swirling flow field, its piezoelectric properties can be effectively activated, achieving the dual goals of pollutant degradation and energy recovery.

[0064] In some embodiments, the three-layer cylinder includes an inner cylinder, a middle cylinder, and an outer cylinder that are coaxially nested. The internal space of the inner cylinder forms the overflow cavity, the annular space between the inner cylinder and the middle cylinder forms the inlet cavity, and the annular space between the middle cylinder and the outer cylinder forms the underflow cavity. The swirl core tube passes through the inlet cavity and is fixed to the inner cylinder and the middle cylinder by a flange connector.

[0065] In these embodiments, the main structure of the swirl oscillating hydrogen generator 6 includes a vertical cylindrical container with three coaxially nested cylinders inside, namely an inner cylinder, a middle cylinder and an outer cylinder, which share the same central axis to form a highly integrated chamber partition system.

[0066] The inner cylinder is a closed circular tube structure, and its internal space forms an overflow cavity for collecting and exporting the light product: hydrogen.

[0067] The annular gap between the inner cylinder and the middle cylinder forms the inlet cavity, which serves as the feed channel for the mixture of methanol-rich solution and piezoelectric catalyst. The annular gap between the middle cylinder and the outer cylinder forms an underflow cavity, which is used to collect and discharge the heavy phase liquid flow containing catalyst particles.

[0068] The swirl core tube runs through the entire inlet chamber, with its upper end extending to near the top of the inner cylinder and its lower end approaching the bottom of the container. The swirl core tube is arranged at an angle, and its side wall has a tangential inlet, which is connected to the first branch of the diversion unit through an inlet pipe located below the inlet chamber.

[0069] To ensure the structural stability of the cyclone core tube under high-speed fluid impact, its two ends are rigidly fixed to the top plate of the inner cylinder and the bottom ring of the middle cylinder via flange connections. This flange connection not only provides mechanical support but also allows for quick disassembly of the cyclone core tube during maintenance, facilitating catalyst replacement or equipment maintenance.

[0070] During operation, a methanol-rich solution enters the cyclone core tube through a tangential inlet at a flow rate of 1.5-3.0 m / s, forming a strong swirling flow field under the combined action of centrifugal force and shear force. Hydrogen gas, due to its low density, rises along the axial low-pressure zone, passes through the top opening of the inner cylinder into the overflow chamber, and is finally discharged from the top overflow port; while the liquid phase carrying catalyst particles is thrown outward by centrifugal force, passes through the bottom end of the cyclone core tube into the underflow chamber, and is discharged into the settling tank 8 from the bottom underflow port.

[0071] The three-layer coaxial cylindrical structure achieves spatial isolation and process integration of the feed, overflow, and underflow channels, avoiding gas-liquid backmixing and solid entrainment, significantly improving hydrogen purity and catalyst recovery rate, while simplifying the overall equipment layout and facilitating system miniaturization and modular deployment.

[0072] In some embodiments, the swirl oscillating hydrogen generator is a multi-stage parallel structure, with the first branch inlet of each stage of the swirl oscillating hydrogen generator connected to the branch pipeline, the overflow outlet of each stage of the swirl oscillating hydrogen generator connected to the hydrogen collection device, and the underflow outlet of each stage of the swirl oscillating hydrogen generator connected to the settling tank 8.

[0073] In practical industrial applications, to adapt to the wastewater flow rates generated by coal chemical alcohol-containing plants of different scales, this invention provides a multi-stage parallel structure micro-vortex hydrogen production and self-Fenton pollutant degradation unit.

[0074] The cyclone oscillating hydrogen generator 6 is not a single device, but rather a parallel assembly of N stages (N≥2) of identical cyclone oscillating hydrogen generators. Each stage of the cyclone oscillating hydrogen generator includes the three-layer cylindrical structure, cyclone core tube, and piezoelectric catalyst system described in the preceding embodiments, and possesses independent feeding, gas phase overflow, and liquid phase underflow functions.

[0075] The specific connection method is as follows: The first branch inlet of each stage of the cyclone oscillating hydrogen generator is connected to the same branch pipeline (i.e., the main branch pipeline from the liquid phase outlet of the thermal regeneration tower 3) through its respective feed branch pipe, and the feed rate of each branch is balanced through a flow distribution valve (such as a proportional regulating valve or orifice plate). The overflow port at the top of each stage of the cyclone oscillating hydrogen generator is connected to the hydrogen collection device through a gas manifold to ensure that the generated hydrogen is collected, purified and stored uniformly. The underflow port at the bottom of each stage of the cyclone oscillating hydrogen generator is connected to the settling tank 8 through a liquid manifold to allow the catalyst-containing liquid phase to be concentrated for solid-liquid separation and catalyst recovery.

[0076] By adjusting the number of parallel stages, the upstream wastewater output can be flexibly matched, avoiding the manufacturing and operational difficulties caused by excessively large single units. When any stage of equipment is under maintenance or malfunctions, the remaining stages can continue to operate, ensuring system continuity. All underflows converge into the same settling tank 8, facilitating unified recycling, regeneration, and reinjection, reducing maintenance complexity. Due to the identical structure of each branch and uniform feed distribution, the vortex intensity, shear stress, and catalytic efficiency within each stage are highly consistent, ensuring stable overall treatment performance.

[0077] The above implementation shows that the multi-level parallel structure not only realizes the engineering scale-up of the technical solution of the present invention, but also significantly improves the system's flexibility, reliability and industrial applicability.

[0078] In some embodiments, the bottom of the settling tank 8 is provided with a catalyst outlet, which is connected to the inlet pipe of the cyclone oscillating hydrogen generator 6 through a return pipeline with a delivery pump to form a catalyst circulation loop; the top or upper side wall of the settling tank 8 is provided with a purified water outlet.

[0079] In these embodiments, the settling tank 8 is not only used to achieve solid-liquid separation, but also integrates the function of automatic catalyst recovery and recycling, forming a closed-loop material flow, which significantly improves the system's economy and environmental protection.

[0080] The settling tank 8 is a conical-bottomed cylindrical container with a catalyst outlet at its bottom. This outlet is connected to the inlet pipe (i.e., upstream of the first branch feed end) of the cyclone oscillator hydrogen generator 6 via a return pipeline equipped with a transfer pump. This forms a catalyst circulation loop: the catalyst-containing slurry discharged from the underflow of the hydrocyclone enters the settling tank 8, and the catalyst particles settle to the conical bottom area under gravity; when the sedimentation amount reaches a set threshold (which can be triggered by a level gauge or timer control), the transfer pump is started to pressurize and send the high-concentration catalyst slurry back to the inlet of the cyclone oscillator hydrogen generator 6, where it mixes with fresh methanol-rich wastewater and participates in the reaction again.

[0081] Optionally, the delivery pump is a diaphragm metering pump or a screw pump, which has corrosion resistance and anti-clogging characteristics, and can adjust the return flow rate according to the system load to ensure that the catalyst concentration in the hydrocyclone is maintained in the optimized range of 0.5-3.0 g / L.

[0082] Meanwhile, the top or upper side wall of the settling tank 8 is equipped with a purified water outlet. The supernatant after sufficient settling (i.e., the treated effluent) is discharged from this outlet. Its COD is usually below 600 mg / L and its B / C ratio is greater than 0.4. It can be directly introduced into the subsequent biological treatment unit, or reused in the plant's circulating cooling water system after simple deep treatment.

[0083] This design effectively solves the industry pain points of traditional catalytic wet oxidation or hydrogen production processes, such as the difficulty in separating catalysts, easy loss, and the need for frequent replenishment, and realizes in-situ regeneration and long-term stable operation of catalysts.

[0084] In some embodiments, the hydrogen collection device includes a cyclone gas-liquid separator 5, a gas dryer, and a hydrogen storage tank 7 connected in sequence. The inlet of the cyclone gas-liquid separator 5 is connected to the overflow port, and the liquid phase outlet of the cyclone gas-liquid separator 5 flows back to the settling tank 8 or is discharged as purified water.

[0085] In these embodiments, to improve the purity of hydrogen products and achieve efficient recovery of entrained droplets, the hydrogen collection device adopts a three-stage series structure, which includes, in sequence: a cyclone gas-liquid separator 5, a gas dryer, and a hydrogen storage tank 7.

[0086] The specific connection relationships are as follows: The inlet of the cyclone gas-liquid separator 5 is connected to the overflow port at the top of the cyclone oscillating hydrogen generator 6 via a gas pipeline, receiving wet hydrogen gas containing trace amounts of droplets (mainly water and trace amounts of methanol). Inside the cyclone gas-liquid separator 5, the wet hydrogen gas enters tangentially and forms a high-speed rotating flow field. Centrifugal force throws the droplets against the wall of the separator, where they coalesce into a liquid film and are discharged along the conical bottom. The liquid phase outlet of the cyclone gas-liquid separator 5 is connected to the settling tank 8 via a return pipeline, returning the separated condensate to the system for unified solid-liquid separation and water quality control. In some operating modes, if the condensate is tested and found to have a COD below 100 mg / L and no catalyst residue, it can be directly discharged as purified water or reused in other water-related processes within the plant. After initial dehydration, the hydrogen enters the gas dryer from the top outlet of the cyclone gas-liquid separator 5. The dryer is filled with molecular sieves (such as type 3A or 4A) or silica gel adsorbent to further remove residual moisture and reduce the hydrogen dew point to below −40°C. The dried high-purity hydrogen is introduced into hydrogen storage tank 7, and can be further purified for use in fuel cells, hydrogenation reactions or sold externally.

[0087] Even if a very small amount of nano-catalyst is entrained, it will be captured in the cyclone gas-liquid separator 5 and returned to the settling tank 8. Reusing the condensate reduces fresh water consumption, aligning with green chemical engineering principles. The dried hydrogen avoids condensation corrosion or ice blockage problems during storage and transportation.

[0088] In some embodiments, the cyclone core tube has an angle of 110° to 120° with the vertical direction.

[0089] In these embodiments, the cyclone core tube in the cyclone oscillator 6 is not installed vertically, but rather its axis is arranged at an obtuse angle to the vertical direction. Specifically, the angle between the axis of the cyclone core tube and the vertical direction is 110° to 120°, that is, its actual tilt angle (relative to the horizontal plane) is 30° to 20° downward.

[0090] When a methanol-rich solution enters the cyclone core tube tangentially from the bottom inlet, a moderate tilt extends the spiral path of the fluid within the core tube, enhancing the swirl development and preventing short-circuit flow caused by vertical installation. A tilt angle of 110°-120° maintains strong centrifugal force while providing a smoother channel for hydrogen to rise along the low-pressure axial region, reducing bubble entrainment to the underflow. The tilted arrangement makes it easier for the sheet-like piezoelectric catalyst to form a non-vertical orientation in the cyclone field, and under the coupling of gravity and centrifugal force, it produces periodic tumbling and deformation, which is beneficial for the continuous excitation of the piezoelectric potential. A slight downward tilt helps high-density catalyst particles slide towards the underflow inlet, preventing accumulation at the end of the core tube.

[0091] Experimental comparisons show that under the same inlet flow rate and catalyst concentration: When the included angle is 90°, the hydrogen entrainment droplet rate is high and the underflow catalyst recovery rate is low. When the included angle is 115°, the hydrogen purity increases, the droplet entrainment rate decreases, the catalyst recovery rate increases, and the COD removal efficiency improves.

[0092] Therefore, controlling the angle between the axis of the cyclone core tube and the vertical direction within the range of 110° to 120° is a key structural parameter for achieving synergistic optimization of efficient hydrogen production, deep degradation, and reliable solid-liquid separation.

[0093] like Figure 4 As shown, in some embodiments, this application also provides a method for treating coal chemical alcohol-containing wastewater that integrates cyclone hydrogen production and self-degradation of Fenton pollutants, applied to the system described in any one of the above embodiments, comprising the following steps: S100: The methanol-rich solution from the coal chemical alcohol-containing unit is fed into flash tank 1 for flash evaporation, and then sequentially passed into reabsorption tower 2 and thermal regeneration tower 3 to remove methanol. and A methanol-rich solution after deacidification was obtained.

[0094] A methanol-rich solution from the alcohol-containing unit of a coal chemical plant is fed into flash tank 1 for flash evaporation at atmospheric pressure and 35°C to release most of the dissolved gas. The liquid then sequentially enters reabsorption tower 2 and thermal regeneration tower 3, where residual gases are completely removed through desorption. and .

[0095] S200: The deacidified methanol-rich solution is split, with one part sent to the cyclone gas-liquid separator 5 to be regenerated into lean methanol and returned to the coal chemical alcohol-containing unit, and the other part sent as treatment liquid to the cyclone oscillating hydrogen generator 6.

[0096] For example, the deacidified methanol-rich solution is diverted according to a set mass ratio: A portion of the flow enters the cyclone gas-liquid separator 5 for distillation to obtain lean methanol, which is then returned to the main coal chemical alcohol system for recycling. The other portion of the flow is used as treated liquid and sent to the cyclone oscillating hydrogen generator 6 to participate in the resource recovery reaction.

[0097] S300: Add flake Mo to the treatment solution The piezoelectric catalyst is fed tangentially from the bottom into the cyclone core tube at a flow rate of 1.5 m / s to 3 m / s. The fluid shear force causes the catalyst to generate a piezoelectric effect, and a redox reaction occurs on the catalyst surface, simultaneously achieving hydrogen production and self-Fenton degradation of organic pollutants. The residence time of the mixture in the cyclone core tube is controlled to be 5 s to 20 s.

[0098] S400: Utilizing the negative pressure environment at the center of the swirling flow field, the generated hydrogen gas migrates towards the axis and is discharged from the overflow port, and is collected after gas-liquid separation; the catalyst and the liquid after reaction move towards the side wall under the action of centrifugal force and are discharged from the bottom outlet.

[0099] Driven by the negative pressure axial region formed at the center of the swirling flow field, the generated hydrogen gas rapidly migrates towards the center, exits from the overflow port, and enters the hydrogen collection device. At the same time, the denser catalyst particles and liquid phase are thrown towards the sidewall under the action of centrifugal force, flow downward along the outside of the swirling core tube, and exit from the underflow port, achieving efficient gas-liquid / solid separation.

[0100] S500: The mixture discharged from the underflow outlet is sent to the settling tank 8 for solid-liquid separation. The recovered catalyst is returned to the cyclone oscillator hydrogen generator 6 for recycling after hydrothermal regeneration. The purified water and hydrogen obtained from the separation can be further utilized as raw materials for the plant.

[0101] In some embodiments, in S300, the self-Fenton degradation process utilizes hydroxyl radicals generated in situ by piezoelectric catalytic water oxidation reaction to degrade organic matter. No additional iron salt catalysts or exogenous hydrogen peroxide are added during the reaction process, and the pH value of the reaction system is the original pH value of the methanol-rich solution after deacidification.

[0102] In all examples shown and described herein, any specific values ​​should be interpreted as merely exemplary and not as limitations; therefore, other examples of exemplary embodiments may have different values.

[0103] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0104] The above-described embodiments are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-degradation of Fenton pollutants, characterized in that, include: The pretreatment and acid gas removal unit includes a flash tank, a reabsorption tower and a thermal regeneration tower connected in sequence along the material flow direction. The flash tank is provided with an inlet for receiving a methanol-rich solution from the coal chemical alcohol-containing unit, and the thermal regeneration tower is provided with a liquid phase outlet. The diversion and regeneration unit includes a diversion pipeline and a cyclone gas-liquid separator. The inlet of the diversion pipeline is connected to the liquid phase outlet of the thermal regeneration tower. The outlet of the diversion pipeline is divided into a first branch and a second branch. A cyclone oscillating hydrogen generator is provided on the first branch. The second branch is connected to the feed inlet of the cyclone gas-liquid separator. The cyclone gas-liquid separator is provided with a regenerated liquid outlet for outputting lean methanol. A cyclone oscillation hydrogen production and self-Fenton pollutant degradation unit includes a cyclone oscillation hydrogen generator. The cyclone oscillation hydrogen generator includes a vertical container, a cyclone core tube, and a three-layer cylinder. The three-layer cylinder divides the inner cavity of the vertical container from the inside to the outside into an overflow cavity, an inlet cavity, and a bottom flow cavity. The cyclone core tube is inclinedly disposed in the inlet cavity. A tangential inlet is provided on the side wall of the cyclone core tube. The tangential inlet is connected to the first branch through an inlet pipe located below the inlet cavity. The top end of the cyclone core tube is connected to the overflow cavity, and the bottom end is connected to the bottom flow cavity. The product separation and resource recovery unit includes a hydrogen collection device and a settling tank. The inlet of the hydrogen collection device is connected to the overflow port at the top of the overflow chamber through a gas pipeline, and the liquid inlet of the settling tank is connected to the bottom outlet at the bottom of the underflow chamber through a liquid pipeline.

2. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-degradation of Fenton pollutants according to claim 1, characterized in that, The inner diameter of the swirling core tube is 10 mm to 50 mm, and the material flow velocity in the inlet tube is controlled between 1.5 m / s and 3 m / s, so that the fluid in the swirling field generates shear stress on the piezoelectric catalyst, inducing the catalyst to deform.

3. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-Fenton pollutant degradation according to claim 2, characterized in that, The piezoelectric catalyst is plate-shaped Mo. Mo-based composite catalyst, the sheet-like Mo When the sheet planes of the composite catalyst move with the fluid, they are not perpendicular to the streamline direction in the swirling flow field. Under the shearing action of the fluid, the catalyst induces lattice distortion and generates a polarized electric field.

4. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-degradation of Fenton pollutants according to claim 1, characterized in that, The three-layer cylinder includes an inner cylinder, a middle cylinder, and an outer cylinder nested coaxially. The internal space of the inner cylinder forms the overflow cavity, the annular space between the inner cylinder and the middle cylinder forms the inlet cavity, and the annular space between the middle cylinder and the outer cylinder forms the underflow cavity. The swirl core tube passes through the inlet cavity and is fixed to the inner cylinder and the middle cylinder by a flange connector.

5. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-degradation of Fenton pollutants according to claim 1, characterized in that, The cyclone oscillating hydrogen generator is a multi-stage parallel structure. The first branch inlet of each stage of the cyclone oscillating hydrogen generator is connected to the branch pipeline. The overflow outlet of each stage of the cyclone oscillating hydrogen generator is connected to the hydrogen collection device. The underflow outlet of each stage of the cyclone oscillating hydrogen generator is connected to the settling tank.

6. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-Fenton pollutant degradation according to claim 1, characterized in that, The bottom of the settling tank is provided with a catalyst outlet, which is connected to the inlet pipe of the cyclone oscillating hydrogen generator through a return pipeline with a delivery pump to form a catalyst circulation loop; the top or upper side wall of the settling tank is provided with a purified water outlet.

7. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-Fenton pollutant degradation according to claim 1, characterized in that, The hydrogen collection device includes a cyclone gas-liquid separator, a gas dryer, and a hydrogen storage tank connected in sequence. The inlet of the cyclone gas-liquid separator is connected to the overflow port, and the liquid phase outlet of the cyclone gas-liquid separator is returned to the settling tank or discharged as purified water.

8. The coal chemical alcohol-containing wastewater treatment system integrating cyclone hydrogen production and self-Fenton pollutant degradation according to claim 1, characterized in that, The cyclone core tube has an angle of 110° to 120° with the vertical direction.

9. A method for treating coal chemical alcohol-containing wastewater integrating cyclone hydrogen production and self-degradation of Fenton pollutants, applied to the system according to any one of claims 1 to 8, characterized in that, Includes the following steps: S100: The methanol-rich solution from the coal chemical alcohol-containing unit is fed into a flash tank for flash evaporation, and then sequentially passed into a reabsorption tower and a thermal regeneration tower to remove methanol. and A deacidified methanol-rich solution was obtained; S200: The deacidified methanol-rich solution is split, with one part sent to a cyclone gas-liquid separator to be regenerated into lean methanol and returned to the coal chemical alcohol-containing unit, and the other part sent as a treatment liquid to a cyclone oscillating hydrogen generator. S300: Add flake Mo to the treatment solution The piezoelectric catalyst is fed tangentially from the bottom into the cyclone core tube at a flow rate of 1.5 m / s to 3 m / s. The fluid shear force generates a polarized electric field in the catalyst, and a redox reaction occurs on the catalyst surface, simultaneously achieving hydrogen production and self-Fenton degradation of organic pollutants. The residence time of the mixture in the cyclone core tube is controlled to be 5 s to 20 s. S400: Utilizing the negative pressure environment at the center of the swirling flow field, the generated hydrogen gas migrates towards the axis and is discharged from the overflow port, and is collected after gas-liquid separation; The catalyst and the reaction liquid settle under gravity and are discharged from the underflow outlet; S5 00: The mixture discharged from the underflow outlet is sent to the settling tank for solid-liquid separation. The recovered catalyst is regenerated by hydrothermal treatment and then returned to the cyclone oscillator for recycling.

10. The method for treating coal chemical alcohol-containing wastewater by integrating cyclone hydrogen production and self-degradation of Fenton pollutants according to claim 9, characterized in that, In S300, the self-Fenton degradation process utilizes piezoelectric catalytic water oxidation reaction to generate hydroxyl radicals in situ to degrade organic matter. No additional iron salt catalysts or exogenous hydrogen peroxide are added during the reaction process, and the pH value of the reaction system is the pH value of the methanol-rich solution after deacidification.

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