CN114804424B - Supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery - Google Patents

Abstract

The invention discloses a supercritical water reaction device integrating enhanced oxidation, online salt removal and waste heat recovery, which comprises an end component, a reactor main body, a bottom head, various heat exchange components, various enhanced oxidation devices and salt removal devices. The complete treatment of organic matters is realized by arranging a catalyst bed layer, a catalytic inner lining, a catalyst adding port and a secondary oxidant/Fenton reagent injection port; the inorganic salt is removed on line by arranging a filtering component, a mechanical scraping device, a tertiary oxidant and subcritical water injection port and a conveying device; the heat exchangers such as the material preheating component, the cooling component and the wall protection component are matched with the heat insulation sleeve, so that waste heat recovery of reaction products is realized in the reactor. The reaction device realizes the coupling of the functions of strengthening oxidation, online salt removal and waste heat recovery, reduces the complexity of the system, improves the economical efficiency and the reliability of the system, and can be widely applied to the technical field of supercritical water reaction.

Description

A supercritical water reaction device integrating enhanced oxidation, on-line desalination, and waste heat recovery

technical field

The invention belongs to the technical field of supercritical water reaction, and relates to a supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery.

Background technique

Supercritical water oxidation technology is a technology that can realize deep oxidation treatment of various organic wastes. The principle of supercritical water oxidation technology is to use supercritical water (T>374.15℃, P>22.12MPa) as the reaction medium, and use its excellent organic/gas dissolution and transfer performance to quickly transform organic matter through a homogeneous oxidation reaction. Stabilize the conversion of CO ₂ , H ₂ O, N ₂ and other harmless small molecules, S, P, etc. into the highest valence salts, so that heavy metals can stably exist in the solid phase residue after mineralization and deposition, and realize the harmlessness of organic waste treatment and resource utilization. Supercritical water oxidation technology has the advantages of high efficiency, thorough treatment, fast reaction rate, and wide application range. It has achieved great success in treating various wastewater and sludge.

When the concentration of organic matter is large enough, the supercritical water oxidation reaction will be more violent, and even produce a hydrothermal flame. This new combustion method is called supercritical hydrothermal combustion, which is a violent oxidation reaction, also known as a flame. Supercritical water oxidation and supercritical hydrothermal combustion technology have good prospects in the treatment of organic hazardous waste.

At present, most of the reactors in the supercritical water reaction system are tubular reactors or simple tank reactors, and the reactor is the core of the supercritical water reaction process device, and its upgrading and improvement has always been the supercritical water reaction technology. research and development focus, but there are still some problems:

(1) In the traditional supercritical water reactor, the high-temperature fluid after reaction is generally led out of the reactor, and then the heat exchanger is used for waste heat recovery. In this way, there are problems such as complex system, large heat exchange surface, and excessive temperature of the reactor wall. And serious corrosion and other defects.

(2) Although the supercritical water oxidation reaction has a good effect on the treatment of organic hazardous waste, it is still difficult to treat the refractory intermediate products such as ammonia nitrogen and acetic acid produced in the reaction process, and requires extremely harsh reaction conditions (high temperature, high pressure, etc.) , long residence time), and this will significantly increase the investment cost of the system and reduce the economy of the system.

(3) Due to the low solubility of salts in supercritical water, it is easy to crystallize and precipitate, resulting in salt deposition, which will block the reactor in severe cases. It is still necessary to further solve the problem of realizing the timely discharge of salts and avoiding the occurrence of salt deposition and blockage. problem.

Therefore, in order to solve the above problems and improve the economy and reliability of the supercritical water reaction system, it is necessary to invent a new type of reaction device.

Contents of the invention

The purpose of the present invention is to solve the problems in the prior art, and provide a supercritical water reaction device integrating enhanced oxidation, online desalination, and waste heat recovery. The present invention arranges some heat exchange devices in the traditional supercritical water reactor device, thermal insulation sleeve, catalyst bed, catalytic inner liner, oxidant/catalyst nozzle, mechanical scraping device, conveying device, etc., to realize the good coupling of the functions of the reaction device, such as enhanced oxidation, online desalting and waste heat recovery, reducing the The complexity of the system improves the economy of the system.

In order to achieve the above object, the present invention adopts the following technical solutions to achieve:

A supercritical water reaction device integrating enhanced oxidation, on-line desalination, and waste heat recovery, including:

Reactor main body, the top of the reactor main body is sealed and connected to the end assembly, and the bottom end is sealed and connected to the bottom head; the inner cavity of the reactor main body is the reaction area, which is used for supercritical water reaction, online desalination and desalination, and waste heat recovery ; A post-reaction fluid outlet is provided on the side wall of the reactor main body;

The end assembly is provided with a supercritical water/auxiliary fuel injection port, a primary oxidant injection port, a material injection port, a catalyst addition port and a secondary oxidant/ Fenton reagent injection port;

Bottom head, the inner cavity of the bottom head is a salt discharge area, the side wall is provided with a third oxidant injection port, and the bottom of the salt discharge area is provided with a salt discharge port.

The further improvement of above-mentioned device is:

The main body of the reactor is provided with a primary cooling assembly, and the outer side of the primary cooling assembly is sequentially provided with a thermal insulation sleeve and a catalyst inner liner; the catalyst inner liner is arranged close to the wall of the reactor main body; the primary cooling assembly is barrel-shaped structure, the top and end components are hermetically connected.

The wall surface of the reactor main body is embedded with a wall surface protection assembly; the wall surface protection assembly is provided with an outlet of the wall surface protection assembly and an inlet of the wall surface protection assembly.

The heat insulation sleeve includes a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder sheathed in sequence, the first heat insulation cylinder is set outside the primary cooling assembly, and the inside of the primary cooling assembly is the primary reaction zone , the part between the inner cavity of the first heat insulation sleeve and the primary cooling assembly is the secondary reaction zone; the part between the first heat insulation cylinder and the second heat insulation cylinder is the tertiary reaction zone; the second heat insulation The part between the cylinder and the third heat insulation cylinder is the fourth-stage reaction zone; the part between the fourth heat insulation cylinder and the catalyst inner liner is the fifth-stage reaction zone;

The bottom of the primary cooling assembly is provided with a filter assembly, and the bottom of the primary reaction zone is communicated with the secondary reaction zone through the filter component; the top of the secondary reaction zone is connected with the tertiary reaction zone; the bottom of the tertiary reaction zone It is connected with the fourth-level reaction zone; the top of the fourth-level reaction zone is connected with the fifth-level reaction zone; the outlet of the reacted fluid is connected with the bottom of the fifth-level reaction zone.

The first-stage reaction zone is provided with a mechanical scraping device, the second reaction zone is provided with a high-temperature catalyst bed, the third reaction zone is provided with a secondary cooling component, and the fourth-stage reaction zone is provided with a material preheating component. A low-temperature catalyst bed, a third-stage cooling assembly, and a post-reaction fluid collector are sequentially arranged in the fifth-stage reaction zone from top to bottom.

An end wall surface temperature control assembly is embedded in the wall surface of the end assembly.

A bottom wall surface temperature control component is arranged on the outer wall surface of the bottom head.

The bottom of the salt discharge area of the bottom head is provided with a conveying device for conveying the reaction product to the salt discharge port, and a subcritical water inlet connected to the salt discharge channel of the conveying device is provided on the side wall of the salt discharge port.

A supercritical water reaction device integrating enhanced oxidation, on-line desalination, and waste heat recovery, comprising the following steps:

When the reactor is in normal operation, the supercritical water/auxiliary fuel enters the reactor from the supercritical water/auxiliary fuel injection port, the material enters the reactor from the material injection port after being preheated by the material preheating component, and the oxidant enters the reactor from the primary oxidant injection port. The preheated material is mixed with oxidant, auxiliary fuel/supercritical water and undergoes supercritical hydrothermal combustion reaction; the high temperature and high pressure reaction product is cooled by the primary cooling component in the primary reaction zone, and then filtered through the filter component, The liquid phase product enters the secondary reaction zone to continue to react, and the solid phase product is deposited in the bottom head;

In the secondary reaction zone, the liquid-phase product passes through the high-temperature catalyst bed and is catalyzed by the catalyst injected from the catalyst addition port to continue to undergo supercritical water catalytic oxidation reaction, and the refractory intermediate product is further degraded, and then the liquid-phase product flows into the tertiary reaction zone ;

In the tertiary reaction zone, the liquid phase product is mixed with the secondary oxidant or Fenton reagent injected from the secondary oxidant/Fenton reagent injection port, and the enhanced oxidation reaction continues to take place; The cooling assembly is cooled, and then the liquid phase product flows into the fourth-stage reaction zone;

In the fourth-stage reaction zone, the liquid-phase product is cooled by the material preheater, and the organic material in the material preheater is preheated, and then the liquid-phase product flows into the fifth-stage reaction zone;

In the fifth-stage reaction zone, the liquid-phase product passes through the catalytic inner liner and the low-temperature catalyst bed for subcritical catalytic oxidation, and the organic matter in the liquid-phase product is further degraded, so that the product can be discharged up to standard; at the same time, the liquid-phase product and the third-stage cooling assembly, The wall protection component performs heat exchange, and the final liquid phase product flows into the post-reaction fluid collector at room temperature and high pressure, and is led out of the reactor through it, and is directly discharged up to standard or reused as reclaimed water;

During the normal operation of the reactor, the mechanical scraping device located in the primary reaction zone continuously removes the inorganic salt deposited on the inner wall of the primary cooling component to prevent salt deposition on the wall; The phase product is separated and enters the bottom head. After being further degraded by three oxidants, it is dissolved by subcritical water, and is continuously discharged from the salt discharge port through the conveying device online.

The above method is further improved in that:

During the normal operation of the reactor, the flow of cooling water is as follows:

Enter from the bottom wall temperature control component on the bottom head to cool the bottom head; then enter the tertiary cooling component, the wall protection component, the top wall temperature control component on the top end cap, the secondary cooling component, and the primary cooling component , to absorb the reaction heat generated during the reaction process of the reactor, and finally the cooling water after heat exchange flows out from the outlet of the primary cooling component; each heat exchange component inside the reactor can be injected with normal temperature and high pressure water to generate supercritical water, or It can be injected with normal temperature and low pressure water to generate steam.

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

1. The present invention can realize the coupling of supercritical hydrothermal combustion reaction of refractory organic waste liquid, high-temperature catalytic oxidation reaction, staged oxidation, Fenton oxidation, low-temperature catalytic oxidation reaction, wall catalytic oxidation and other reactions, and can realize refractory organic waste liquid Harmless treatment and standard discharge of waste liquid.

2. In the present invention, heat exchange components such as material preheating components, cooling components, wall surface protection components, and wall surface temperature control components are used to cooperate with heat insulation sleeves to realize waste heat utilization of high-temperature and high-pressure reaction products in the reactor, reducing heat transfer Loss, while realizing the preheating of cold material.

3. The present invention utilizes the joint use of mechanical desalination device, filter assembly, tertiary oxidant, subcritical water injection port and delivery device to realize the continuous on-line removal of inorganic salts during the reaction process, and at the same time recover the corresponding heat to realize The harmlessness and resource utilization of inorganic salts have been improved.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, 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 thus It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.

Fig. 1 is a schematic sectional view of the structure of the reactor of the present invention.

Among them, 1-end assembly; 2-reactor main body; 3-wall protection assembly; 4-catalytic inner liner; 5-low temperature catalyst bed; 6-tertiary cooling assembly; 7-material preheating assembly; 8- Filter assembly; 9-fluid collector after reaction; 10-bottom head; 11-bottom wall temperature control component; 12-end wall temperature control component; 13-first-stage cooling component; 14-high temperature catalyst bed; 15- Insulation sleeve; 16-mechanical scraping device; 17-secondary cooling assembly; 18-conveying device; 19-first-level reaction zone; 20-secondary reaction zone; 21-third-level reaction zone; ;23-fifth-stage reaction zone; N1-supercritical water/auxiliary fuel injection port; N2-primary oxidant injection port; N3-material injection port; N4-wall protection component outlet; N5-end wall temperature control component inlet ;N6-the outlet of the primary cooling component; N7-the inlet of the primary cooling component; N8-the outlet of the end wall temperature control component; N9-the catalyst addition port; N10-the secondary oxidant/Fenton reagent injection port; N11- Wall protection component inlet; N12-material preheating component outlet; N13-secondary cooling component outlet; N14-tertiary cooling component outlet; N15-secondary cooling component inlet; N16-material preheating component inlet ; N17-the inlet of the tertiary cooling assembly; N18-the outlet of the fluid collector after the reaction; N19-the third oxidant injection port; N20-the outlet of the bottom wall temperature control assembly; N21-the introduction of the bottom wall temperature control assembly; Critical water inlet; N23-salt discharge port.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated in the figures herein may be arranged and designed in a variety of different configurations.

Accordingly, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

It should be noted that like numerals and letters denote similar items in the following figures, therefore, once an item is defined in one figure, it does not require further definition and explanation in subsequent figures.

In the description of the embodiments of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "upper", "lower", "horizontal", "inside" etc. is based on the orientation or positional relationship shown in the drawings , or the orientation or positional relationship that the product of the invention is usually placed in use is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation or be constructed in a specific orientation and operation, and therefore should not be construed as limiting the invention. In addition, the terms "first", "second", etc. are only used for distinguishing descriptions, and should not be construed as indicating or implying relative importance.

In addition, when the term "horizontal" appears, it does not mean that the part is required to be absolutely horizontal, but may be slightly inclined. For example, "horizontal" only means that its direction is more horizontal than "vertical", and it does not mean that the structure must be completely horizontal, but can be slightly inclined.

In the description of the embodiments of the present invention, it should also be noted that, unless otherwise specified and limited, the terms "setting", "installation", "connection" and "connection" should be interpreted in a broad sense, for example, It can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediary, and it can be the internal communication of two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.

The present invention is described in further detail below in conjunction with accompanying drawing:

Referring to FIG. 1 , the embodiment of the present invention discloses a supercritical water reaction device integrating enhanced oxidation, online desalination, and waste heat recovery, including a reactor body 2 , an end assembly 1 and a bottom head 10 .

The top end of the reactor main body 2 is sealed and connected to the end assembly 1, and the bottom end is sealed and connected to the bottom head 10; the inner cavity of the reactor main body 2 is a reaction zone, which is used for supercritical water reaction, on-line desalination and desalination, and waste heat recovery; The side wall of the reactor main body 2 is provided with a post-reaction fluid outlet N18; the reactor main body 2 is provided with a primary cooling assembly 13, and the outer side of the primary cooling assembly 13 is sequentially provided with an insulating sleeve 15 and a catalyst inner sleeve 4; the catalyst inner sleeve 4. It is arranged close to the wall of the reactor main body 2; the primary cooling assembly 13 is a barrel-shaped structure, and the top is sealed with the end assembly 1. A wall protection assembly 3 is embedded in the wall of the reactor main body 2; the wall protection assembly 3 is provided with an outlet N4 of the wall protection assembly and an inlet N11 of the wall protection assembly. The heat insulation sleeve 15 includes a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder sheathed in sequence, the first heat insulation cylinder is set outside the primary cooling assembly 13, and the interior of the primary cooling assembly 13 is a primary reaction zone 19 , the part between the inner cavity of the first heat insulation sleeve and the primary cooling assembly 13 is the secondary reaction zone 20; the part between the first heat insulation cylinder and the second heat insulation cylinder is the tertiary reaction zone 21; the second heat insulation cylinder The part between the third heat insulating cylinder is the fourth-stage reaction zone 22; the part between the fourth heat insulating cylinder and the catalyst inner liner 4 is the fifth-stage reaction zone 21;

The bottom of the primary cooling assembly 12 is provided with a filter assembly 8, and the bottom of the primary reaction zone 19 communicates with the secondary reaction zone 20 through the filter assembly 8; the top of the secondary reaction zone 20 communicates with the tertiary reaction zone 21; The bottom of the reaction zone 21 communicates with the reaction zone 22 of the fourth level; the top of the reaction zone 22 of the fourth level communicates with the reaction zone 23 of the fifth level;

The primary reaction zone 19 is provided with a mechanical scraping device 16, the second reaction zone 20 is provided with a high-temperature catalyst bed 14, the third reaction zone 21 is provided with a secondary cooling assembly 17, and the fourth reaction zone 22 is provided with The material preheating component 7, the low-temperature catalyst bed 5, the tertiary cooling component 6 and the post-reaction fluid concentrator 9 are sequentially arranged in the fifth-stage reaction zone 23 from top to bottom.

The end assembly 1 is provided with a supercritical water/auxiliary fuel injection port N1, a primary oxidant injection port N2, a material injection port N3, a catalyst addition port N9 and a secondary oxidant/ Fenton's reagent injection port N10; the end wall surface temperature control assembly 12 is embedded in the wall surface of the end assembly 1 .

The inner cavity of the bottom head 10 is a salt discharge area, three oxidant injection ports N19 are provided on the side wall, and the salt discharge port N23 is provided at the bottom of the salt discharge area. A bottom wall temperature control assembly 11 is provided on the outer wall of the bottom head 10 . The bottom of the salt discharge area of the bottom head 10 is provided with a conveying device 18, which is used to convey the reaction product to the salt discharge port N23, and a subcritical water jet connected to the salt discharge channel of the conveying device 18 is provided on the side wall of the salt discharge port N23. Entrance N22.

Structural principle of the present invention is as follows:

As shown in Figure 1, the supercritical water reaction device of the present invention integrating enhanced oxidation-online desalination-waste heat recovery includes an end assembly 1, a reactor main body 2 and a bottom head 10; wherein, the end assembly 1 There are end wall temperature control components 12, supercritical water/auxiliary fuel injection port N1, primary oxidant injection port N2, material injection port N3, catalyst addition port N9 and secondary oxidant/Fenton reagent injection port N10; the reactor The wall surface of the main body 2 is provided with a wall surface protection component 3, and the inner side of the wall surface is provided with a catalytic inner liner 4; the inside of the reactor main body 2 is divided into a primary reaction zone 19 and a secondary reaction zone 20 by a thermal insulation sleeve 15 and a primary cooling component 13 , three-stage reaction zone 21, four-stage reaction zone 22, five-stage reaction zone 23; mechanical scraping device 16 is provided in one-stage reaction zone 19, high-temperature catalyst bed 14 is provided in two-stage reaction zone 20, three-stage reaction The zone 21 is provided with a secondary cooling assembly 17, the fourth-stage reaction zone 22 is provided with a material cooling assembly 7, and the fifth-stage reaction zone 23 is provided with a low-temperature catalyst bed 5, a tertiary cooling assembly 6, and a post-reaction fluid collector 9 ; The wall of the bottom head 10 is provided with a tertiary oxidant injection port N19, a bottom wall surface temperature control assembly 11, and the lower part is provided with a conveying device 18, a subcritical water injection port N22 and a salt discharge port N23.

The end wall surface temperature control assembly 12 is provided with an inlet N5 and an outlet N8, the wall protection assembly 3 is provided with an inlet N11 and an outlet N4, the material preheating assembly 7 is provided with an inlet N16 and an outlet N12, and the primary cooling assembly 13 is provided with an inlet N7 and an outlet N6, the secondary cooling assembly 17 is provided with an inlet N15 and an outlet N13, the tertiary cooling assembly 6 is provided with an inlet N17 and an outlet N14, and the post-reaction fluid collector 9 is provided with an outlet Outlet N18, the bottom wall temperature control assembly 11 is provided with an inlet N21 and an outlet N20, and these inlets and outlets can be arranged on the end assembly 1, the reactor main body 2 or the bottom head 15.

The inlets and outlets of the bottom wall surface temperature control assembly 11, the tertiary cooling assembly 6, the wall surface protection assembly 3, the end wall surface temperature control assembly 12, the secondary cooling assembly 17, and the primary cooling assembly 13 are connected in sequence; the internal cold fluid of these heat exchange assemblies It can be cooling water at normal temperature and high pressure, or cooling water at normal temperature and low pressure, and its flow direction is opposite to that of the reaction products in each reaction zone; Shaped tube, coil type, water cooling jacket and other forms.

The positions of the catalyst addition port N9 and the secondary oxidant/Fenton reagent injection port N10 are not limited to the secondary reaction zone 20 and the tertiary reaction zone 21, and can be adjusted according to the properties of the material. The catalytic inner liner 4, the low-temperature catalyst bed 5 and the high-temperature catalyst bed 14 can be disassembled and replaced.

The mechanical scraping device 16 includes, but is not limited to, a stirring scraper; the conveying device 18 includes, but is not limited to, a conveying screw, and the like.

The working process of the present invention is as follows:

When the reactor is in normal operation, the supercritical water/auxiliary fuel enters the reactor from the supercritical water/auxiliary fuel injection port N1, the material enters the reactor from the material injection port N2 after being preheated by the material preheating component 7, and the oxidant enters the reactor from the primary oxidant injection port. The inlet N3 enters the reactor; the preheated material is mixed with oxidant, auxiliary fuel/supercritical water and undergoes supercritical hydrothermal combustion reaction. The high-temperature and high-pressure reaction product is cooled by the primary cooling component 13 in the primary reaction zone 19, and then filtered by the filter component 8. The liquid phase product enters the secondary reaction zone 20 to continue the reaction, and the solid phase products such as salts are deposited at the bottom. Inside the head 10;

In the secondary reaction zone 20, the liquid-phase product is catalyzed by the high-temperature catalyst bed 14 and the catalyst injected from the catalyst addition port N9 to continue the supercritical water catalytic oxidation reaction, and the refractory intermediate products such as ammonia nitrogen are further degraded, and then the liquid-phase product Flow into the tertiary reaction zone 21.

In the tertiary reaction zone 21, the liquid phase product is mixed with the secondary oxidant or Fenton's reagent injected from the secondary oxidant/Fenton's reagent injection port N10, and the enhanced oxidation reaction continues to occur, and the selective injection of the secondary oxidant or Fenton's reagent According to the type and property selection of undegraded substances, at the same time, the liquid phase product is cooled by the secondary cooling assembly 17 in the third-level reaction zone 21, thereby avoiding the material preheater 7 in the fourth-level reaction zone 22 from generating hot walls, resulting in During the preheating process, the organic material in the preheater is deposited with salt and blocks the preheater, and then the liquid phase product flows into the fourth-stage reaction zone 22 .

In the fourth-stage reaction zone 22 , the liquid-phase product is cooled by the material preheater 7 , and the organic material in the material pre-heater 7 is preheated, and then the liquid-phase product flows into the fifth-stage reaction zone 23 .

In the fifth-stage reaction zone 23, the liquid-phase product undergoes subcritical catalytic oxidation through the catalytic inner liner 4 and the low-temperature catalyst bed 5, and a small amount of small molecular organic substances that may still be contained in the liquid-phase product are further completely degraded, so that the product can reach the standard at one time Discharge; at the same time, the liquid phase product exchanges heat with the tertiary cooling assembly 6 and the wall surface protection assembly 3, and the final liquid phase product flows into the post-reaction fluid collector 13 at normal temperature and high pressure and is drawn out of the reactor through it, and is discharged directly to the standard or reclaimed water Reuse.

During the normal operation of the reactor, the flow of cooling water is as follows: enter from the bottom wall temperature control component 11 on the bottom head 10 to cool the bottom head 10; then enter the tertiary cooling component 6, wall protection component 3, top The top wall temperature control component 12, the secondary cooling component 17, and the primary cooling component 13 on the end cover 1 absorb the reaction heat generated during the reaction process of the reactor, and finally the cooling water after heat exchange is exported from the primary cooling component N6 outflow. Each heat exchange component inside the reactor can be injected with normal temperature and high pressure water to generate supercritical water, and can also be injected with normal temperature and low pressure water to generate steam.

During the normal operation of the reactor, the mechanical scraping device 16 located in the primary reaction zone 19 continuously removes the inorganic salts deposited on the inner wall surface of the primary cooling assembly 13 to prevent salt deposition on the wall surface; the role of inorganic salts in the filter assembly 8 Next, it is separated from the liquid phase product and enters the bottom head 10. After being further degraded by the oxidant three times, it is dissolved by subcritical water, and is continuously discharged from the salt discharge port N23 through the conveying device 18 online.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (7)

1. A supercritical water reaction device integrating enhanced oxidation, online desalination, and waste heat recovery, characterized in that it includes a reactor main body (2) and an end component (1); The top end of the reactor main body (2) is sealed to the end assembly (1), and the bottom end is sealed to the bottom head (10); the inner cavity of the reactor main body (2) is a reaction zone for supercritical water reaction , on-line desalination and desalination and waste heat recovery; a post-reaction fluid outlet (N18) is provided on the side wall of the reactor main body (2); a primary cooling assembly (13) is arranged inside the reactor main body (2), and the primary cooling assembly (13) The heat insulating sleeve (15) and the catalyst inner liner (4) are sequentially set on the outer side; the catalyst inner liner (4) is set close to the wall of the reactor main body (2); the primary cooling component (13) is Barrel-shaped structure, the top and the end assembly (1) are hermetically connected; The end assembly (1) is provided with a supercritical water/auxiliary fuel injection port (N1), a primary oxidant injection port (N2), and a material injection port ( N3), catalyst addition port (N9) and secondary oxidant/Fenton reagent injection port (N10); The inner cavity of the bottom head (10) is a salt discharge area, three oxidant injection ports (N19) are provided on the side wall, and a salt discharge port (N23) is provided at the bottom of the salt discharge area; The heat insulation sleeve (15) includes a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder sheathed in sequence, the first heat insulation cylinder is set outside the primary cooling assembly (13), and the primary cooling assembly (13) The interior is a primary reaction zone (19), and the part between the inner cavity of the first heat insulation sleeve and the primary cooling assembly (13) is a secondary reaction zone (20); the first heat insulation cylinder and the second The part between the two heat-insulating cylinders is the third-stage reaction zone (21); the part between the second heat-insulating cylinder and the third heat-insulating cylinder is the fourth-stage reaction zone (22); the fourth heat-insulating cylinder and the catalyst lining The part between the sets (4) is the fifth-level reaction zone (21); The bottom of the primary cooling assembly (12) is provided with a filter assembly (8), and the bottom of the primary reaction zone (19) communicates with the secondary reaction zone (20) through the filter component (8); the secondary reaction zone ( The top of 20) is connected with the third-level reaction zone (21); the bottom of the third-level reaction zone (21) is connected with the fourth-level reaction zone (22); the top of the fourth-level reaction zone (22) is connected with the fifth-level reaction zone ( 23) are connected; after the reaction, the fluid outlet (N18) is connected with the bottom of the fifth-stage reaction zone (23); The first-stage reaction zone (19) is provided with a mechanical scraping device (16), the second reaction zone (20) is provided with a high-temperature catalyst bed (14), and the third reaction zone (21) is provided with a secondary The cooling assembly (17), the material preheating assembly (7) is installed in the fourth-stage reaction area (22), the low-temperature catalyst bed (5) and the third-stage cooling assembly are arranged in the fifth-stage reaction area (23) from top to bottom (6) and post-reaction fluid collector (9). 2. The supercritical water reaction device integrating enhanced oxidation, online desalting, and waste heat recovery according to claim 1, characterized in that, the wall surface of the reactor body (2) is embedded with a wall surface protection component (3) ; The wall protection assembly (3) is provided with a wall protection assembly outlet (N4) and a wall protection assembly inlet (N11). 3. The supercritical water reaction device integrating enhanced oxidation, online desalination, and waste heat recovery according to claim 1, characterized in that, the wall surface of the end assembly (1) is embedded with an end wall surface temperature control assembly (12). 4. The supercritical water reaction device integrating enhanced oxidation, online desalting, and waste heat recovery according to claim 1, characterized in that, the outer wall surface of the bottom head (10) is provided with a bottom wall surface temperature control component (11). 5. The supercritical water reaction device integrating enhanced oxidation, online desalination and waste heat recovery according to claim 1 or 4, characterized in that, the bottom of the bottom head (10) in the salt discharge area is provided with a conveying device (18), used to transport the reaction product to the salt discharge port (N23), the side wall of the salt discharge port (N23) is provided with a subcritical water injection port (N22) connected to the salt discharge channel of the delivery device (18). 6. A supercritical water reaction method adopting the set enhanced oxidation of the device described in any one of claims 1-5, on-line desalting, waste heat recovery, characterized in that, comprising the following steps: When the reactor is in normal operation, the supercritical water/auxiliary fuel enters the reactor from the supercritical water/auxiliary fuel injection port (N1), and the material enters the reactor from the material injection port (N2) after being preheated by the material preheating component (7) , the oxidant enters the reactor from the primary oxidant injection port (N3); the preheated material mixes with the oxidant, auxiliary fuel/supercritical water and undergoes supercritical hydrothermal combustion reaction; the high temperature and high pressure reaction product is in the primary reaction zone (19 ) is cooled by the primary cooling component (13), and then filtered by the filter component (8), the liquid phase product enters the secondary reaction zone (20) to continue to react, and the solid phase product is deposited in the bottom head (10); In the secondary reaction zone (20), the liquid-phase product is catalyzed by the high-temperature catalyst bed (14) and the catalyst injected from the catalyst addition port (N9) to continue the supercritical water catalytic oxidation reaction, and the refractory intermediate product is further degraded, Then the liquid phase product flows into the tertiary reaction zone (21); In the tertiary reaction zone (21), the liquid phase product is mixed with the secondary oxidant or Fenton reagent injected from the secondary oxidant/Fenton reagent injection port (N10), and the enhanced oxidation reaction continues to take place; The first reaction zone (21) is cooled by the second cooling assembly (17), and then the liquid phase product flows into the fourth reaction zone (22); In the fourth-stage reaction zone (22), the liquid-phase product is cooled by the material preheater (7), and the organic material in the material preheater (7) is preheated, and then the liquid-phase product flows into the fifth-stage reaction zone (23); In the fifth-stage reaction zone (23), the liquid phase product undergoes subcritical catalytic oxidation through the catalytic inner liner (4) and the low-temperature catalyst bed (5), and the organic matter in the liquid phase product is further degraded, so that the product can meet the discharge standard; at the same time The liquid-phase product exchanges heat with the tertiary cooling component (6) and the wall surface protection component (3), and the final liquid-phase product flows into the post-reaction fluid collector (9) at room temperature and high pressure, and is led out of the reactor through it, and is directly discharged up to the standard or reclaimed water; During the normal operation of the reactor, the mechanical scraping device (16) located in the primary reaction zone (19) continuously removes the inorganic salt deposited on the inner wall surface of the primary cooling component (13) to prevent salt deposition on the wall surface; Under the action of the filter assembly (8), it is separated from the liquid phase product and enters the bottom head (10). After being further degraded by the oxidant three times, it is dissolved by subcritical water, and is continuously conveyed from The salt discharge port (N23) discharges. 7. The supercritical water reaction method that integrates enhanced oxidation, on-line desalting, and waste heat recovery according to claim 6, characterized in that, during the normal operation of the reactor, the flow process of the cooling water is as follows: Enter from the bottom wall temperature control component (11) on the bottom head (10), cool the bottom head (10); then enter the tertiary cooling component (6), wall protection component (3), top end cover (1 ), the top wall temperature control component (12), the secondary cooling component (17), and the primary cooling component (13) absorb the reaction heat generated during the reaction process of the reactor, and finally the cooling water after heat exchange flows from the primary The outlet (N6) of the cooling component flows out; each heat exchange component inside the reactor can be injected with normal temperature and high pressure water to generate supercritical water, and can also be injected with normal temperature and low pressure water to generate steam.

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