A heat exchange-reaction integrated supersubcritical water oxidation reactor and method

Abstract

The present invention discloses a heat exchange-reaction integrated super-subcritical water oxidation reactor and method. The reactor includes an outer cylinder, an inner cylinder, and a lower support plate therein. A water storage chamber is formed between the lower support plate and the bottom of the outer cylinder. The interior of the inner cylinder is divided into a catalytic reaction zone and a preheating heat exchange zone by the upper support plate. The preheating heat exchange zone is provided with a plurality of heat exchange tubes arranged in an array. The upper ends of the heat exchange tubes are connected to the catalytic reaction zone, and the lower ends of the heat exchange tubes are connected to the water storage chamber. The lower end of the central guide tube is connected to the preheating heat exchange zone, and the upper end of the central guide tube upwardly passes through the catalyst bed in the catalytic reaction zone. The outer cylinder is provided with a material inlet and a material outlet. The raw material liquid introduced from the material inlet can enter the preheating heat exchange zone and contact the outer wall of the heat exchange tube for heat exchange. The present invention combines a conventional heat exchanger and a super-subcritical reactor into an independent structure that integrates heat exchange and oxidation reaction functions, occupies a small area, and reduces the price of reactor materials.

Description

Technical Field

[0001] The present invention relates to the technical field of super subcritical water oxidation in the environmental protection industry, and in particular to a heat exchange-reaction integrated super subcritical water oxidation reactor and method. Background Art

[0002] Supercritical-Subcritical Water oxidation (SUW) is a green, efficient, advanced oxidation technology. It offers significant technical advantages and broad application prospects in the treatment of industrial wastewater and waste. Subcritical water oxidation refers to the oxidation reaction of materials in subcritical water (subcritical water refers to a state where the temperature and pressure of water are lower than the critical water temperature or critical water pressure, and the density is greater than the critical water density). Subcritical water oxidation, to a certain extent, shares the advantages of supercritical water oxidation, which is rapid and efficient, while maintaining less stringent oxidation conditions.

[0003] In the process of using subcritical water oxidation technology to treat high-salt and high-concentration organic wastewater, since the reaction needs to be carried out under high temperature and high pressure conditions, there may be some problems: first, the reaction cylinder will rust, causing equipment damage and failure; second, the heat of the high-temperature reaction liquid after the reaction cannot be efficiently utilized; third, the equipment manufacturing cost is high; fourth, the equipment occupies a large area.

[0004] Therefore, when treating high-salt and high-concentration organic wastewater, we can achieve the following goals through reasonable design of processes and equipment: (1) Recover reaction heat by using high-temperature reaction liquid to heat the materials to be reacted, improve heat utilization, achieve heat self-sufficiency, and reduce operating costs; (2) Reduce the use of high-value corrosion-resistant and high-temperature resistant metal materials, which not only avoids corrosion of the cylinder, but also reduces the manufacturing cost of the equipment; (3) Make full use of space resources and reduce the equipment's footprint. Summary of the Invention

[0005] To address the aforementioned technical issues in the prior art, the present application aims to provide a supercritical water oxidation reactor and method that integrates heat exchange and reaction. This invention combines a conventional heat exchanger and a supercritical water oxidation reactor into a single, independent structure that combines heat exchange and oxidation reaction functions. First, this reduces floor space, reduces the risk of equipment leakage, and reduces the use of expensive materials. Second, it improves the space utilization of the equipment and the heat utilization of the reaction liquid. Ultimately, this can reduce the manufacturing and operating costs of supercritical water oxidation equipment.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A heat exchange-reaction integrated supersubcritical water oxidation reactor comprises an outer cylinder and an inner cylinder and a lower support plate arranged from top to bottom inside the outer cylinder, a water storage chamber is formed between the lower support plate and the bottom of the outer cylinder; an upper support plate is arranged inside the inner cylinder and is divided by the upper support plate into a catalytic reaction zone above and a preheating heat exchange zone below, a porous support plate is arranged at the bottom of the inner cylinder, and the catalytic reaction zone is provided with a catalyst bed; a plurality of heat exchange tubes arranged in an array are arranged in the preheating heat exchange zone, and the preheating heat exchange zone outside the heat exchange tube is the shell-side heat exchange chamber, the upper end of the heat exchange tube is connected to the upper support plate and communicates with the catalytic reaction zone, and the lower end of the heat exchange tube passes through the porous support plate and is connected to the lower support plate and communicates with the water storage chamber; the outer cylinder is divided into an upper area and a lower area by the lower support plate, and at the same time, the upper area of ​​the outer cylinder and the inner cylinder are divided into two relatively independent functional areas by the porous support plate.

[0008] A central flow guide pipe is further provided in the center of the catalytic reaction zone, the lower end of which is connected to the upper support plate and communicates with the preheating heat exchange zone, and the upper end of the central flow guide pipe passes upward through the catalyst bed; a material inlet and a material outlet are provided on the outer cylinder, and the raw material liquid introduced from the material inlet can flow through the area above the lower support plate, pass through the porous support plate, enter the preheating heat exchange zone, and contact the outer wall of the heat exchange tube for heat exchange; the material outlet is communicated with the water storage chamber;

[0009] An oxidant disperser is also provided in the lower end of the outer cylinder and is arranged close to the upper part of the lower support plate.

[0010] The diversion chamber and reaction liquid distribution buffer chamber are located above and below the catalyst bed, respectively. The diversion chamber primarily allows for further mixing of the reactants and oxidant, achieving optimal treatment results. The reaction liquid distribution buffer chamber primarily reduces the material's water exit velocity and increases its residence time within the heat exchange tubes, ensuring sufficient heat exchange between the high-temperature reaction liquid and the relatively low-temperature reactants within the shell-side heat exchange chamber, achieving efficient heat recovery and reuse.

[0011] Furthermore, the catalyst bed includes a perforated support plate and an oxidation catalyst particle layer filled and stacked on the upper surface of the perforated support plate. The perforated support plate and the upper support plate are spaced apart and a reaction liquid distribution buffer chamber is formed therebetween. The upper surface of the oxidation catalyst particle layer and the inner wall of the top of the inner cylinder are spaced apart and a diversion chamber is formed therebetween. The central guide pipe passes through the center of the oxidation catalyst particle layer and its upper port extends into the diversion chamber.

[0012] The catalyst bed is located in the upper area of ​​the inner cylinder. The catalyst is supported by a perforated support plate with a central flow guide pipe in the middle. After being heated in the shell-side heat exchange chamber, the reacted materials flow along the central flow guide pipe into the diversion chamber and then into the catalyst bed for reaction. This allows the materials to fully react and ensures the water quality of the effluent.

[0013] The water storage chamber is located in the lower area of ​​the outer cylinder. The high-temperature reaction liquid inside the heat exchange tube enters the water storage chamber after heat exchange in the shell-side heat exchange chamber. The cooled reaction liquid is buffered in the water storage chamber and then enters the next cooling system from the material outlet.

[0014] Furthermore, the heat exchange tube is connected to the upper support plate, the porous support plate and the lower support plate as a whole by welding.

[0015] Furthermore, a gap is provided between the outer wall of the inner cylinder and the inner wall of the outer cylinder, and a heater is provided in the annular gap between the gap to preheat the raw material liquid flowing through; the material inlet is provided at the top of the upper end of the outer cylinder, and the raw material liquid introduced from the material inlet reaches the lower support plate along the annular gap between the outer wall of the inner cylinder and the inner wall of the outer cylinder, mixes with the oxidant sprayed from the oxidant disperser, and then passes through the porous support plate into the shell-side heat exchange chamber of the inner cylinder to obtain heat through heat exchange.

[0016] Furthermore, an upper end cap and a lower end cap are installed at the top and bottom of the outer cylinder, respectively. Both the upper end cap and the lower end cap are circular cap structures and are detachably connected to the two ends of the outer cylinder. The upper end cap and the lower end cap are first placed in the corresponding grooves at the two ends of the outer cylinder, and then connected and sealed to the outer cylinder through the fixing effect of the hollow circular cover and bolts. The lower end cap located in the lower area of ​​the outer cylinder is provided with a drainage channel for discharging the materials after the reaction.

[0017] Furthermore, the outer cylinder is made of a material that is resistant to high pressure but not resistant to high temperature. Ordinary stainless steel is generally selected, such as ferritic stainless steel, and the inner wall is coated with an anti-corrosion coating; the inner cylinder is relatively in a high-temperature environment, and generally uses an alloy material with high heat resistance and better corrosion resistance. The material may not be resistant to high pressure, for example, titanium alloy can be selected.

[0018] The heat exchange tubes in the present invention have both the function of guiding flow and the function of transferring heat. The high-temperature reaction liquid after the reaction heats the materials to be reacted before the reaction, thus achieving self-heating.

[0019] The catalyst bed is arranged in the upper section inside the inner cylinder, and the catalyst can be replaced from time to time, and different types of catalysts can also be replaced according to reaction requirements.

[0020] Furthermore, the oxidant disperser includes a mosquito coil and a liquid inlet branch connected thereto, a plurality of liquid outlet holes are evenly arranged on the top of the mosquito coil, the mosquito coil is arranged in the outer cylinder near the top of the lower support plate, and one end of the liquid inlet branch passes through the side wall of the outer cylinder.

[0021] A subcritical water catalytic oxidation method adopts the aforementioned heat exchange-reaction integrated supersubcritical water oxidation reactor for reaction, introduces raw material liquid into a material inlet, and the raw material liquid contacts and mixes with the oxidant released by the oxidant disperser when reaching the top of the lower support plate, and then enters the shell heat exchange chamber through the channels on the porous support plate, and the oxidant and the material to be reacted obtain heat through heat exchange and are heated, thereby accelerating the reaction; the mixed liquid then enters the catalyst bed in the catalytic reaction zone through a central guide pipe for oxidation reaction, and the oxidation reaction releases heat to heat the reaction liquid, and the generated high-temperature reaction liquid evenly drips onto the upper support plate and enters the interior of the heat exchange tube, and the high-temperature reaction liquid inside the heat exchange tube exchanges heat with the material to be reacted and the oxidant in the shell heat exchange chamber, heating the material to be reacted and the oxidant, thereby achieving heat recovery and reuse; after heat transfer in the shell heat exchange chamber, the high-temperature reaction liquid finally reaches the water storage chamber and is discharged through the material outlet.

[0022] Furthermore, the raw material liquid is high-salt and high-concentration organic wastewater, for example, pharmaceutical wastewater, that is, high COD (50,000-100,000 mg / L) organic wastewater with a salt content of 4wt%-15wt%.

[0023] The catalytic oxidation method of the present invention has the following characteristics: 1. The high-temperature fluid after the reaction can heat the raw material liquid to the temperature required for the reaction by passing through the heat exchange chamber; 2. The catalyst bed further undergoes an oxidation reaction (lowering the temperature required for the reaction and releasing a large amount of heat), which makes the fluid temperature after the catalyst bed reaction much higher than the temperature of the liquid to be reacted, thereby achieving self-heating and reducing the heat provided by the outside.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The reactor of the present invention is provided with two inner and outer cylinders with different functions, one is an outer cylinder that is resistant to high pressure but not to high temperature, and the other is an inner cylinder for the subcritical water oxidation reaction and heat exchange of organic wastewater. The inner cylinder is not resistant to high pressure but resistant to high temperature and corrosion. The relatively low-temperature reactant enters the shell-side heat exchange chamber, and the high-temperature reaction liquid generated by the supercritical oxidation reaction enters the interior of the heat exchange tube. The high-temperature reaction liquid inside the heat exchange tube transfers the heat it carries to the reactant outside the tube wall through its tube wall, that is, heat exchange occurs with the reactant and oxidant in the shell-side heat exchange chamber, so that the material outside the guide tube wall reaches the temperature required for the reaction. The reactor fully utilizes the reaction heat after the subcritical water oxidation reaction, achieves heat recovery and reuse, realizes self-heating of the reaction, and can even output heat (steam) for the oxidation reaction of high-concentration organic wastewater, reducing the cost required for external heating, thereby reducing the operating cost of the equipment.

[0026] 2) The present invention combines a conventional heat exchanger and a super-subcritical reactor into an independent structure that integrates heat exchange and oxidation reaction functions. Since the reactor is an integrated structure, first, it avoids the large floor space required by the use of multiple instruments and equipment, greatly improving the space utilization rate of the equipment and the heat utilization rate of the reaction liquid; second, it reduces the risk of leakage caused by the connection between multiple instruments and equipment; third, the material requirement for the outer cylinder of the integrated reactor is that it may not be resistant to high temperatures but must be resistant to high pressures; the material requirement for the inner wall of the inner cylinder and the pipes inside the inner cylinder is that it may not be resistant to high pressures but must be resistant to high temperatures and corrosion. This reduces the use of expensive corrosion-resistant and high-temperature-resistant materials and, to a certain extent, also reduces the manufacturing cost of the equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic structural diagram of a heat exchange-reaction integrated super-subcritical water oxidation reactor of the present invention;

[0028] Among them: 01. Upper end cover; 02. Bolt; 03. Hollow circular cover; 04. Outer cylinder; 05. Insulation layer; 06. Heat exchange tube; 07. Porous support plate; 08. Oxidant disperser; 09. Material outlet; 10. Material inlet; 11. Diversion chamber; 12. Catalyst bed; 13. Central guide tube; 14. Perforated support plate; 15. Inner cylinder; 16. Reaction liquid distribution buffer chamber; 17. Upper support plate; 18. Shell-side heat exchange chamber; 19. Lower support plate; 20. Water storage chamber; 21. Lower end cover. DETAILED DESCRIPTION

[0029] The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0030] Referring to the accompanying examples of the present invention, Figure 1 , more clearly and completely describes the example embodiments disclosed in the present invention. The described embodiments are part of the embodiments of the present invention, not all of the embodiments. In addition, the technical features involved in different implementations of the present invention can be combined with each other as long as they do not conflict with each other. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0031] An embodiment of the present invention provides a heat exchange-reaction integrated supersubcritical water oxidation reactor, comprising: an upper end cover 01, an outer cylinder 04, an inner cylinder 15, a plurality of built-in heat exchange tubes 06, a diversion chamber 11, a catalyst bed 12, a reaction liquid distribution buffer chamber 16, an oxidant disperser 08, a water storage chamber 20, and a lower end cover 21.

[0032] The upper end cover head 01 and the lower end cover head 21 are respectively installed on the top and bottom of the outer cylinder 04. The upper end cover head 01 and the lower end cover head 21 are both circular cover head structures and can be detachably connected to the two ends of the outer cylinder 04; the upper end cover head 01 and the lower end cover head 21 are first placed in the corresponding grooves at the two ends of the outer cylinder 04, and then the upper end cover head 01 and the lower end cover head 21 are connected and sealed to the outer cylinder 04 through the fixing action of the hollow circular cover 03 and the bolts 02.

[0033] An inner cylinder 15 is positioned within the outer cylinder 04, running along the center of the inner cavity. The upper region of the outer cylinder 04 and the inner cylinder 15 are divided into two relatively independent functional zones by a porous support plate 07. The outer cylinder 04 is further divided into an upper region and a lower region by a lower support plate 19. The upper region formed between the upper end cap 01 and the lower support plate 19 provides space for material preheating, heat exchange, and reaction. The lower end cap 21 and the lower support plate 19 form a water storage chamber 20.

[0034] An upper support plate 17 is provided inside the inner cylinder 15 and is divided into an upper catalytic reaction zone and a lower preheating heat exchange zone by the upper support plate 17. A porous support plate 07 is provided at the bottom of the inner cylinder 15, and the catalytic reaction zone is provided with a catalyst bed 12; a plurality of arrayed heat exchange tubes 06 are provided in the preheating heat exchange zone, and the preheating heat exchange zone outside the heat exchange tube 06 is the shell-side heat exchange chamber 18, the upper end of the heat exchange tube 06 is connected to the upper support plate 17 and communicated with the catalytic reaction zone, and the lower end of the heat exchange tube 06 passes through the porous support plate 07 and is connected to the lower support plate 19 and communicated with the water storage chamber 20.

[0035] The catalyst bed 12 includes a perforated support plate 14 and an oxidation catalyst particle layer filled and stacked on the upper surface of the perforated support plate 14. The perforated support plate 14 and the upper support plate 17 are spaced apart to form a reaction liquid distribution buffer chamber 16 therebetween. The upper surface of the oxidation catalyst particle layer and the inner wall of the top of the inner cylinder 15 are spaced apart to form a diversion chamber 11 therebetween.

[0036] A central flow guide pipe 13 is provided at the center of the catalytic reaction zone, and the lower end of the central flow guide pipe 13 is connected to the upper support plate 17 and communicated with the preheating heat exchange zone, that is, the lower end of the central flow guide pipe 13 is communicated with the shell-side heat exchange chamber 18. The upper end of the central flow guide pipe 13 passes upward through the catalyst bed 12, and the central flow guide pipe 13 passes through the center of the oxidation catalyst particle layer and its upper end extends into the diversion chamber 11. The outer cylinder 04 is provided with a material inlet 10 and a material outlet 9. The raw material liquid introduced from the material inlet 10 can flow through the porous support plate 07 through the area above the lower support plate 19, enter the preheating heat exchange zone, and contact with the outer wall of the heat exchange pipe 06 for heat exchange; the material outlet 9 is communicated with the water storage chamber 20; comparison Figure 1 The material outlet 9 is arranged in the lower end cover 21.

[0037] A gap is set between the outer wall of the inner cylinder 15 and the inner wall of the outer cylinder 04. The material inlet 10 is set at the top of the upper end of the outer cylinder 04. The raw material liquid introduced from the material inlet 10 reaches the lower support plate 19 along the annular gap between the outer wall of the inner cylinder 15 and the inner wall of the outer cylinder 04, mixes with the oxidant sprayed from the oxidant disperser 08, and then passes through the porous support plate 07 into the shell-side heat exchange chamber 18 of the inner cylinder 15 to obtain heat through heat exchange.

[0038] An oxidant disperser 08 is further provided in the lower end of the outer cylinder 04 and is provided close to the upper portion of the lower support plate 19. The heat exchange tube 06 is integrally connected to the upper support plate 17, the porous support plate 07 and the lower support plate 19 by welding.

[0039] After being preheated in the annular gap between the outer cylinder 04 and the inner cylinder 15, the raw material liquid reaches the bottom of the upper area of ​​the outer cylinder 04, and then is blocked by the lower support plate 19 and mixed with the oxidant sprayed from the oxidant disperser 08. It then passes through the porous support plate 07 and enters the shell-side heat exchange chamber 18 of the inner cylinder 15 to obtain heat and reach the temperature required for the subcritical water oxidation reaction. It then enters the diversion chamber 11 through the central guide pipe 13 of the inner cylinder 15 to react, and finally enters the catalyst bed 12 for further catalytic oxidation reaction; the high-temperature reaction liquid then enters the built-in heat exchange pipe 06 through the perforated support plate 14, and then enters the water storage chamber 20 along the heat exchange pipe 06, and finally reaches the material outlet 09.

[0040] The outer cylinder 04 is also provided with an insulation layer 5. The outer cylinder is made of a material that is resistant to high pressure but not high temperature, generally made of ordinary stainless steel, such as ferritic stainless steel, with an anti-corrosion coating on the inner wall. The inner cylinder is in a relatively high temperature environment and is generally made of an alloy material with high heat resistance and better corrosion resistance. The material may not be resistant to high pressure, such as titanium alloy.

[0041] In some preferred embodiments, the upper area of ​​the reactor is separated into two functional areas by a porous support plate 07. The porous support plate 07 allows the mixed reactant material and oxidant to enter the shell-side heat exchange chamber 18. Since the porous support plate 07 has several fine holes, the amount of reactant passing through the porous support plate 07 per unit time becomes smaller, thereby increasing the residence time of the reactant material and oxidant in the shell-side heat exchange chamber 18, allowing the reactant material and oxidant to fully exchange heat with the high-temperature reaction liquid, so that the temperature of the reactant material reaches the temperature required for the reaction.

[0042] In some preferred embodiments, the porous support plate 07 is a thin metal plate with fine pores having an area equal to the cross-sectional area of ​​the inner cylinder 15 , and is fixed to the side wall of the inner cylinder 15 by welding part of its edge.

[0043] In some preferred embodiments, the built-in heat exchange tube 06 is fixed by the upper support plate 17 , the porous support plate 07 and the lower support plate 19 .

[0044] In some preferred embodiments, the oxidant disperser 08 includes a mosquito coil-type coil and a liquid inlet branch pipe connected thereto. A plurality of liquid outlet holes are evenly arranged on the top of the mosquito coil-type coil. The mosquito coil-type coil is arranged in the outer cylinder 04 close to the top of the lower support plate 19, and one end of the liquid inlet branch pipe passes through the side wall of the outer cylinder 04.

[0045] In some preferred embodiments, the catalyst bed 12 is fixed between the perforated support plate 14 and the diversion chamber 11, and the solid catalyst required for the reaction is laid in the catalyst bed 12, so that the material undergoes a catalytic oxidation reaction in the bed, and the reacted material further enters the reaction liquid distribution buffer chamber 16.

[0046] In some preferred embodiments, both the heat exchange tubes 06 and the central flow guide tube 13 are specially designed, corrosion-resistant, and high-temperature-resistant straight metal tubes. Heat exchange tubes 06 are evenly distributed within the inner cylinder 15 and secured by an upper support plate 17, a porous support plate 07, and a lower support plate 19. Their upper portions communicate with the reaction liquid distribution buffer chamber 16, their middle portions extend through the shell-side heat exchange chamber 18, and their lower portions communicate with the water storage chamber 20. Central flow guide tube 13 extends from the center of the cylinder through the catalyst bed, with its lower end connected to the heat exchange chamber 18 and its upper end extending into and communicating with the diversion chamber 11.

[0047] The present invention also provides an embodiment of a subcritical water oxidation method, which uses the heat exchange-reaction integrated supercritical water oxidation reactor in the above embodiment, comprising the following steps:

[0048] The raw material liquid is introduced into the material inlet 10, and after being preheated along the annular gap between the outer cylinder 04 and the inner cylinder 15, it reaches the bottom of the lower area of ​​the outer cylinder 04;

[0049] The material is blocked by the lower support plate 19 and mixed with the oxidant sprayed from the oxidant disperser 08. Then, it enters the shell-side heat exchange chamber 18 through the pores on the porous support plate 07. The oxidant and the reacted material obtain heat in the shell-side heat exchange chamber 18 and reach the required reaction temperature.

[0050] The mixed reactants pass through the central flow guide pipe 13 again and enter the diversion chamber 11 and the catalyst bed 12 for oxidation reaction. The high-temperature reaction liquid after the oxidation reaction enters the heat exchange pipe 06, where heat exchange occurs in the shell-side heat exchange chamber 18, transferring the heat to the reactants, thereby achieving heat recovery and reuse.

[0051] After the high-temperature reaction liquid passes through the shell-side heat exchange chamber 18 for heat transfer, it finally reaches the water storage chamber 20 and then enters the next system through the material outlet 09.

[0052] The lower support plate 19, the upper support plate 17, the perforated support plate 14 and the porous support plate 07 are all made of special corrosion-resistant and high-temperature resistant metal materials, and are fixed in the corresponding cylinder by welding.

[0053] The contents described in this specification are merely an enumeration of the implementation forms of the inventive concept, and the protection scope of the present invention should not be considered as being limited to the specific forms described in the embodiments.

Claims

1. A heat exchange-reaction integrated super subcritical water oxidation reactor, characterized in that: The invention comprises an outer cylinder (04) and an inner cylinder (15) and a lower support plate (19) arranged in an interval from top to bottom inside the outer cylinder (04), wherein a water storage chamber (20) is formed between the lower support plate (19) and the bottom of the outer cylinder (04); an upper support plate (17) is arranged inside the inner cylinder (15) and is divided into an upper catalytic reaction zone and a lower preheating heat exchange zone by the upper support plate (17); a porous support plate (07) is arranged at the bottom of the inner cylinder (15), and the catalytic reaction zone is provided with a catalyst bed (12); a plurality of arrayed heat exchange tubes (06) are arranged in the preheating heat exchange zone, and the preheating heat exchange zone outside the heat exchange tube (06) is a shell-side heat exchange chamber (18); the upper end of the heat exchange tube (06) is connected to the upper support plate (17) and communicates with the catalytic reaction zone, and the lower end of the heat exchange tube (06) passes through the porous support plate (07) and is connected to the lower support plate (19) and communicates with the water storage chamber (20); A central flow guide pipe (13) is further provided at the center of the catalytic reaction zone, the lower end of the central flow guide pipe (13) being connected to the upper support plate (17) and communicating with the preheating heat exchange zone, and the upper end of the central flow guide pipe (13) passing upward through the catalyst bed (12); a material inlet (10) and a material outlet (9) are provided on the outer cylinder (04); the raw material liquid introduced from the material inlet (10) can flow through the porous support plate (07) through the area above the lower support plate (19), enter the preheating heat exchange zone, and contact the outer wall of the heat exchange pipe (06) for heat exchange; the material outlet (9) is communicated with the water storage chamber (20); An oxidant disperser (08) is also provided in the lower end of the outer cylinder (04), and the oxidant disperser (08) is provided close to the upper part of the lower support plate (19).

2. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: The catalyst bed (12) comprises a perforated support plate (14) and an oxidation catalyst particle layer filled and stacked on the upper surface of the perforated support plate (14); the perforated support plate (14) and the upper support plate (17) are spaced apart and a reaction liquid distribution buffer chamber (16) is formed therebetween; the upper surface of the oxidation catalyst particle layer and the inner wall of the top of the inner cylinder (15) are spaced apart and a diversion chamber (11) is formed therebetween; the central flow guide pipe (13) passes through the center of the oxidation catalyst particle layer and its upper end extends into the diversion chamber (11).

3. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: The heat exchange tube (06) is connected to the upper support plate (17), the porous support plate (07) and the lower support plate (19) as a whole by welding.

4. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: A gap is provided between the outer wall of the inner cylinder (15) and the inner wall of the outer cylinder (04), and a heater is provided in the annular gap between the gap to preheat the raw material liquid flowing through; the material inlet (10) is provided at the top of the upper end of the outer cylinder (04), and the raw material liquid introduced from the material inlet (10) reaches the lower support plate (19) along the annular gap between the outer wall of the inner cylinder (15) and the inner wall of the outer cylinder (04), mixes with the oxidant sprayed from the oxidant disperser (08), and then passes through the porous support plate (07) into the shell-side heat exchange chamber (18) of the inner cylinder (15) to obtain heat through heat exchange.

5. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: An upper end cover (01) and a lower end cover (21) are respectively installed on the top and bottom of the outer cylinder (04). The upper end cover (01) and the lower end cover (21) are both circular cover structures and are detachably connected to the two ends of the outer cylinder (04). The upper end cover (01) and the lower end cover (21) are first placed in corresponding grooves at the two ends of the outer cylinder (04), and then the upper end cover (01) and the lower end cover (21) are connected and sealed to the outer cylinder (04) through the fixing action of the hollow circular cover (03) and the bolts (02).

6. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: The outer cylinder (04) is made of a material that is resistant to high pressure but not resistant to high temperature, and is made of ferritic stainless steel, with the inner wall surface coated with an anti-corrosion coating; the inner cylinder (15) is made of a material that is resistant to heat preservation corrosion but not resistant to high pressure, and is made of titanium alloy.

7. The heat exchange-reaction integrated super subcritical water oxidation reactor according to claim 1, characterized in that: The oxidant disperser (08) includes a mosquito coil and a liquid inlet branch connected thereto. A plurality of liquid outlet holes are evenly arranged on the top of the mosquito coil. The mosquito coil is arranged in the outer cylinder (04) near the top of the lower support plate (19). One end of the liquid inlet branch passes through the side wall of the outer cylinder (04).

8. A subcritical water catalytic oxidation method, characterized in that A heat exchange-reaction integrated super subcritical water oxidation reactor according to any one of claims 1 to 7 is used for reaction, wherein a raw material liquid is introduced into the material inlet (10), and the raw material liquid reaches the upper part of the lower support plate (19) and contacts and mixes with the oxidant released by the oxidant disperser (08), and then enters the shell heat exchange chamber (18) through the channel on the porous support plate (07), and the oxidant and the material to be reacted obtain heat through heat exchange and then heat up to the temperature required for the reaction, thereby accelerating the reaction; the mixed liquid then passes through the central guide pipe (13) and is discharged through the upper port of the central guide pipe (13) to the The heat overflows from all sides and enters the catalyst bed (12) in the catalytic reaction zone for oxidation reaction. The oxidation reaction releases heat to heat the reaction liquid, and the generated high-temperature reaction liquid evenly drips onto the upper support plate (17) and enters the inside of the heat exchange tube (06). The high-temperature reaction liquid inside the heat exchange tube (06) exchanges heat with the materials to be reacted and the oxidant in the shell-side heat exchange chamber (18), heating the materials to be reacted and the oxidant, thereby achieving heat recovery and reuse. After the high-temperature reaction liquid transfers heat in the shell-side heat exchange chamber (18), it finally reaches the water storage chamber (20) and is discharged through the material outlet (09).

9. A subcritical water catalytic oxidation method according to claim 8, characterized in that The raw material liquid is high-salt and high-concentration organic sewage.

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