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

Supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery Download PDF

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CN114804424B
CN114804424B CN202210466791.1A CN202210466791A CN114804424B CN 114804424 B CN114804424 B CN 114804424B CN 202210466791 A CN202210466791 A CN 202210466791A CN 114804424 B CN114804424 B CN 114804424B
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reaction zone
component
stage
supercritical water
reactor
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CN114804424A (en
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王树众
李建娜
刘凯
孙圣瀚
王进龙
刘伟
刘璐
杨闯
李艳辉
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/10—Energy recovery
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

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

Supercritical water reaction device integrating enhanced oxidation, online desalting 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 salt removal and waste heat recovery.
Background
Supercritical water oxidation technology is a technology that can realize advanced oxidation treatment of various organic wastes. The principle of supercritical water oxidation technology is thatWater boundary (T)>374.15℃，P>22.12 MPa) is used as a reaction medium, and the excellent organic matter/gas dissolution and transmission performance of the reaction medium is utilized to rapidly convert the organic matter into CO through homogeneous oxidation reaction 2 、H 2 O、N 2 And other harmless micromolecules, S, P and the like are converted into the highest valence salts for stabilization, so that the heavy metals are stably present in the solid phase residues after mineralization and deposition, and the harmless treatment and the recycling of the organic wastes are realized. The supercritical water oxidation technology has the advantages of high efficiency, thorough treatment, high reaction rate, wide application range and the like, and has been successful in treating various waste water and sludge.
When the concentration of organic matters is large enough, supercritical water oxidation reaction can be more severe, even hydrothermal flame can be generated, the novel combustion mode is called supercritical water combustion, is a severe oxidation reaction, is also called flame supercritical water oxidation, and the supercritical water combustion technology has a good prospect in the aspect of treating organic hazardous waste.
At present, most of reactors in a supercritical water reaction system are tubular reactors or simple kettle reactors, and the reactors are used as cores in supercritical water reaction process devices, so that the upgrading and improvement of the reactors are always development emphasis of supercritical water reaction technology, but at present, some problems still exist:
(1) The traditional supercritical water reactor generally leads the reacted high-temperature fluid out of the reactor, and then the heat exchanger is used for recovering waste heat, so that the defects of complex system, larger heat exchange surface, serious corrosion of the wall surface of the reactor due to overhigh temperature and the like exist.
(2) Although supercritical water oxidation has good treatment effect on organic hazardous waste, organic matters such as ammonia nitrogen, acetic acid and the like which are refractory intermediate products generated in the reaction process are still difficult to treat, extremely harsh reaction conditions (high temperature, high pressure and long residence time) are required, so that the investment cost of a system can be obviously increased, and the economical efficiency of the system is reduced.
(3) Because the solubility of the salt in supercritical water is low, the salt is easy to crystallize and separate out, salt deposition is caused, the reactor is blocked when serious, and the problems of timely discharging the salt, avoiding the salt deposition and blocking are still further solved.
Therefore, in order to solve the above problems and to improve the economy and reliability of supercritical water reaction systems, it is necessary to invent a novel reaction apparatus.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a supercritical water reaction device integrating the functions of enhanced oxidation, on-line desalination, waste heat recovery and the like.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
supercritical water reaction unit integrating enhanced oxidation, online desalting and waste heat recovery, comprising:
the reactor comprises a reactor main body, wherein the top end of the reactor main body is connected with an end component in a sealing way, and the bottom end of the reactor main body is connected with a bottom seal head in a sealing way; the inner cavity of the reactor main body is a reaction zone for carrying out supercritical water reaction, on-line desalination and salt removal and waste heat recovery; the side wall of the reactor main body is provided with a reacted fluid outlet;
the end part component is provided with a supercritical water/auxiliary fuel injection port, a primary oxidant injection port, a material injection port, a catalyst adding port and a secondary oxidant/Fenton reagent injection port which are all communicated with a reaction zone of the inner cavity of the reactor main body;
the inner cavity of the bottom seal head is a salt discharging area, the side wall is provided with a tertiary oxidant injection port, and the bottom of the salt discharging area is provided with a salt discharging port.
The device is further improved in that:
a primary cooling assembly is arranged in the reactor main body, and a heat insulation sleeve and a catalyst inner bushing are sleeved outside the primary cooling assembly in sequence; the catalyst inner lining is closely attached to the wall surface of the reactor main body; the first-stage cooling component is of a barrel-shaped structure, and the top of the first-stage cooling component is in sealing connection with the end component.
A wall protection component is embedded in the wall of the reactor main body; the wall protection assembly is provided with a wall protection assembly outlet and a wall protection assembly inlet.
The heat insulation sleeve comprises a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder which are sleeved in sequence, the first heat insulation cylinder is sleeved outside the primary cooling assembly, a primary reaction zone is arranged inside the primary cooling assembly, and a secondary reaction zone is arranged between the inner cavity of the first heat insulation cylinder sleeve and the primary cooling assembly; the part between the first heat-insulating cylinder and the second heat-insulating cylinder is a three-stage reaction zone; the part between the second heat-insulating cylinder and the third heat-insulating cylinder is a four-stage reaction zone; the part between the fourth heat insulation cylinder and the catalyst inner lining is a five-stage reaction zone;
the bottom of the primary cooling component is provided with a filtering component, and the bottom of the primary reaction zone is communicated with the secondary reaction zone through the filtering component; the top of the secondary reaction zone is communicated with the tertiary reaction zone; the bottom of the third-stage reaction zone is communicated with the fourth-stage reaction zone; the top of the four-stage reaction zone is communicated with the five-stage reaction zone; the fluid outlet after the reaction is communicated with the bottom of the five-stage reaction zone.
The device comprises a first-stage reaction zone, a second-stage reaction zone, a third-stage reaction zone, a material preheating component, a fifth-stage reaction zone, a high-temperature catalyst bed layer, a third-stage cooling component and a reacted fluid collector.
The end wall surface temperature control assembly is embedded in the wall surface of the end assembly.
The outer wall surface of the bottom seal head is provided with a bottom wall surface temperature control assembly.
The bottom of the bottom seal head salt discharging area is provided with a conveying device for conveying reaction products to a salt discharging port, and a subcritical water injection port communicated with a salt discharging channel of the conveying device is formed in the side wall of the salt discharging port.
A supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery comprises the following steps:
when the reactor normally operates, supercritical water/auxiliary fuel enters the reactor from a supercritical water/auxiliary fuel injection port, materials enter the reactor from a material injection port after being preheated by a material preheating component, and oxidant enters the reactor from a primary oxidant injection port; mixing the preheated material with an oxidant, auxiliary fuel/supercritical water and generating a supercritical hydrothermal combustion reaction; the high-temperature and high-pressure reaction product is cooled by the primary cooling component in the primary reaction zone, then filtered by the filtering 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 second-stage reaction zone, the liquid-phase product is catalyzed by a high-temperature catalyst bed layer and a catalyst injected from a catalyst adding port to continuously perform supercritical water catalytic oxidation reaction, the nondegradable intermediate product is further degraded, and then the liquid-phase product flows into the third-stage reaction zone;
in the third-stage 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 intensified oxidation reaction is continued to occur; simultaneously, the liquid-phase product is cooled by a secondary cooling assembly in a tertiary reaction zone, and then the liquid-phase product flows into a quaternary reaction zone;
in the fourth-stage reaction zone, the liquid-phase product is cooled by a material preheater, organic materials in the material preheater are preheated, and then the liquid-phase product flows into a fifth-stage reaction zone;
in the fifth-stage reaction zone, the liquid-phase product is subjected to subcritical catalytic oxidation through the catalytic inner lining and the low-temperature catalyst bed layer, and organic matters in the liquid-phase product are further degraded, so that the product can reach the emission standard; meanwhile, the liquid phase product exchanges heat with the three-stage cooling assembly and the wall protection assembly, and finally the liquid phase product flows into the reacted fluid collector in a normal temperature and high pressure state and is led out of the reactor through the fluid collector, and is directly discharged after reaching standards or recycled water is recycled;
in the normal operation process of the reactor, the mechanical scraping device positioned in the primary reaction zone continuously removes inorganic salt deposited on the inner wall surface of the primary cooling component, so that the salt deposition on the wall surface is prevented; inorganic salt is separated from liquid-phase products under the action of a filtering component, enters into a bottom sealing head, is further degraded by a tertiary oxidant, is dissolved by subcritical water, and is continuously discharged from a salt discharging port on line through a conveying device.
The method is further improved in that:
during normal operation of the reactor, the flow of cooling water is as follows:
entering from a bottom wall temperature control assembly on the bottom seal head, and cooling the bottom seal head; then sequentially entering a three-stage cooling assembly, a wall protection assembly, a top wall temperature control assembly on a top end cover, a second-stage cooling assembly and a first-stage cooling assembly, absorbing reaction heat generated in the reaction process of the reactor, and finally enabling cooling water subjected to heat exchange to flow out from an outlet of the first-stage cooling assembly; the heat exchange components in the reactor can be filled with normal-temperature high-pressure water to generate supercritical water or normal-temperature low-pressure water to generate steam.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can realize the coupling of reactions such as supercritical hydrothermal combustion reaction, high-temperature catalytic oxidation reaction, sectional oxidation, fenton oxidation, low-temperature catalytic oxidation reaction, wall catalytic oxidation and the like of the refractory organic waste liquid, and can realize the harmless treatment and standard emission of the refractory organic waste liquid.
2. According to the invention, the heat exchange components such as the material preheating component, the cooling component, the wall protection component, the wall temperature control component and the like are matched with the heat insulation sleeve, so that the waste heat utilization of high-temperature high-pressure reaction products is realized in the reactor, the heat exchange loss is reduced, and meanwhile, the preheating of cold materials is realized.
3. The invention realizes continuous online removal of inorganic salt in the reaction process by using the combination of the mechanical desalting device, the filtering component, the tertiary oxidant, the subcritical water injection port and the conveying device, and simultaneously recovers corresponding heat, thereby realizing harmless and recycling of the inorganic salt.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of the reactor of the present invention.
Wherein, 1-end assembly; 2-a reactor body; 3-a wall protection assembly; 4-catalytic inner liner; 5-a low temperature catalyst bed; 6-a three-stage cooling assembly; 7-a material preheating assembly; 8-a filter assembly; 9-a post-reaction fluid collector; 10-bottom head; 11-a bottom wall temperature control assembly; 12-an end wall temperature control assembly; 13-a primary cooling assembly; 14-a high temperature catalyst bed; 15-an insulating sleeve; 16-mechanical scraping means; 17-a secondary cooling assembly; 18-a conveying device; 19-a first stage reaction zone; a 20-second stage reaction zone; 21-third stage reaction zone; 22-fourth stage reaction zone; 23-five stages of reaction zones; n1-supercritical water/auxiliary fuel injection port; n2-primary oxidant injection port; n3-material injection port; an N4-wall protection assembly outlet; n5-an inlet of the end wall temperature control assembly; n6-a primary cooling assembly outlet; n7-a primary cooling assembly inlet; n8-outlet of the end wall temperature control assembly; n9-catalyst addition port; n10-secondary oxidant/fenton reagent injection port; n11-wall protection assembly inlet; n12 is a material preheating component outlet; an N13-secondary cooling module outlet; n14-three-stage cooling module outlet; an N15-secondary cooling module inlet; n16-a material preheating assembly inlet; n17-three stage cooling module inlet; n18-outlet of fluid collector after reaction; an N19-tertiary oxidant injection port; n20 is a bottom wall surface temperature control assembly outlet; n21-a bottom wall temperature control assembly inlet; an N22-subcritical water injection port; n23-salt discharging port.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the embodiments of the present invention, it should be noted that, if the terms "upper," "lower," "horizontal," "inner," and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or the azimuth or the positional relationship in which the inventive product is conventionally put in use, it is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
Furthermore, the term "horizontal" if present does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 1, the embodiment of the invention discloses a supercritical water reaction device integrating enhanced oxidation, online salt removal and waste heat recovery, which comprises a reactor main body 2, an end assembly 1 and a bottom head 10.
The top end of the reactor main body 2 is connected with the end component 1 in a sealing way, and the bottom end is connected with the bottom seal head 10 in a sealing way; the inner cavity of the reactor main body 2 is a reaction zone for supercritical water reaction, on-line desalination and salt removal and waste heat recovery; the side wall of the reactor main body 2 is provided with a reacted fluid outlet N18; a primary cooling assembly 13 is arranged in the reactor main body 2, and a heat insulation sleeve 15 and a catalyst inner bushing 4 are sleeved outside the primary cooling assembly 13 in sequence; the catalyst inner lining 4 is closely attached to the wall surface of the reactor main body 2; the primary cooling assembly 13 is in a barrel-shaped structure, and the top of the primary cooling assembly is in sealing connection with the end assembly 1. The wall surface of the reactor main body 2 is embedded with a wall surface protection component 3; the wall protection unit 3 is provided with a wall protection unit outlet N4 and a wall protection unit inlet N11. The heat insulation sleeve 15 comprises a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder which are sleeved in sequence, the first heat insulation cylinder is sleeved outside the primary cooling assembly 13, a primary reaction zone 19 is arranged inside the primary cooling assembly 13, and a secondary reaction zone 20 is arranged between the inner cavity of the first heat insulation cylinder and the primary cooling assembly 13; the part between the first heat insulation cylinder and the second heat insulation cylinder is a three-stage reaction zone 21; the portion between the second and third adiabatic cylinders is a four-stage reaction zone 22; the part between the fourth heat-insulating cylinder and the catalyst inner lining 4 is a five-stage reaction zone 21;
the bottom of the primary cooling component 12 is provided with a filter component 8, and the bottom of the primary reaction zone 19 is communicated with a secondary reaction zone 20 through the filter component 8; the top of the secondary reaction zone 20 is communicated with the tertiary reaction zone 21; the bottom of the third-stage reaction zone 21 is communicated with a fourth-stage reaction zone 22; the top of the four-stage reaction zone 22 is in communication with a five-stage reaction zone 23; the post-reaction fluid outlet N18 communicates with the bottom of the five-stage reaction zone 23.
The mechanical scraping device 16 is arranged in the first-stage reaction zone 19, the high-temperature catalyst bed layer 14 is arranged in the second reaction zone 20, the second-stage cooling component 17 is arranged in the third reaction zone 21, the material preheating component 7 is arranged in the fourth-stage reaction zone 22, and the low-temperature catalyst bed layer 5, the third-stage cooling component 6 and the reacted fluid collector 9 are sequentially arranged in the fifth-stage reaction zone 23 from top to bottom.
The end component 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 adding port N9 and a secondary oxidant/Fenton reagent injection port N10 which are all communicated with a reaction zone in the inner cavity of the reactor main body 2; the end wall temperature control assembly 12 is embedded in the wall of the end assembly 1.
The inner cavity of the bottom seal head 10 is a salt discharging area, the side wall is provided with a tertiary oxidant injection opening N19, and the bottom of the salt discharging area is provided with a salt discharging opening N23. The outer wall surface of the bottom seal head 10 is provided with a bottom wall surface temperature control assembly 11. The bottom of the salt discharging area of the bottom sealing head 10 is provided with a conveying device 18 for conveying reaction products to a salt discharging port N23, and a subcritical water injection port N22 communicated with a salt discharging channel of the conveying device 18 is formed in the side wall of the salt discharging port N23.
The invention has the following structural principle:
as shown in fig. 1, the supercritical water reaction device integrating the functions of enhanced oxidation, online salt removal and waste heat recovery comprises an end component 1, a reactor main body 2 and a bottom seal head 10; wherein, the end component 1 is provided with an end wall surface temperature control component 12, a supercritical water/auxiliary fuel injection port N1, a primary oxidant injection port N2, a material injection port N3, a catalyst adding port N9 and a secondary oxidant/Fenton reagent injection port N10; the wall surface of the reactor 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 lining 4; the inside of the reactor main body 2 is divided into a first-stage reaction zone 19, a second-stage reaction zone 20, a third-stage reaction zone 21, a fourth-stage reaction zone 22 and a fifth-stage reaction zone 23 by a heat-insulating sleeve 15 and a first-stage cooling component 13; the first-stage reaction zone 19 is internally provided with a mechanical scraping device 16, the second-stage reaction zone 20 is internally provided with a high-temperature catalyst bed layer 14, the third-stage reaction zone 21 is internally provided with a second-stage cooling component 17, the fourth-stage reaction zone 22 is internally provided with a material cooling component 7, and the fifth-stage reaction zone 23 is internally provided with a low-temperature catalyst bed layer 5, a third-stage cooling component 6 and a reacted fluid collector 9; the wall surface of the bottom sealing head 10 is provided with a tertiary oxidant injection opening N19 and a bottom wall surface temperature control assembly 11, and the lower part is provided with a conveying device 18, a subcritical water injection opening N22 and a salt discharging opening N23.
The end wall 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, 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, the fluid collector 9 is provided with an outlet N18 after reaction, the bottom wall temperature control assembly 11 is provided with an inlet N21 and an outlet N20, and the inlets and the outlets can be arranged on the end assembly 1, the reactor main body 2 or the bottom head 15.
The bottom wall temperature control assembly 11, the three-stage cooling assembly 6, the wall protection assembly 3, the end wall temperature control assembly 12, the secondary cooling assembly 17 and the inlet and outlet of the primary cooling assembly 13 are sequentially connected; the internal cold fluid of the heat exchange assemblies can be normal-temperature high-pressure cooling water or normal-temperature low-pressure cooling water, and the flow direction of the internal cold fluid is opposite to the flow direction of reaction products in each reaction zone; forms of these heat exchange assemblies and material preheating assemblies include, but are not limited to, membrane wall, serpentine, coil, water jacket, and the like.
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 may be adjusted according to the material properties. The catalytic inner liner 4, the low temperature catalyst bed 5, and the high temperature catalyst bed 14 may be removed and replaced.
Mechanical scraping means 16 include, but are not limited to, forms of stirring scrapers or the like; the conveying means 18 includes, but is not limited to, a conveyor screw or the like.
The working process of the invention is as follows:
when the reactor normally operates, supercritical water/auxiliary fuel enters the reactor from a supercritical water/auxiliary fuel injection port N1, materials enter the reactor from a material injection port N2 after being preheated by a material preheating component 7, and oxidant enters the reactor from a primary oxidant injection port N3; the preheated material is mixed with oxidant and auxiliary fuel/supercritical water and subjected to supercritical hydrothermal combustion reaction. The high-temperature and high-pressure reaction products are cooled by the primary cooling component 13 in the primary reaction zone 19, then filtered by the filtering component 8, and the liquid-phase products enter the secondary reaction zone 20 to continue to react, and solid-phase products such as salts are deposited in the bottom seal 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 adding port N9 to continue supercritical water catalytic oxidation reaction, the refractory intermediate products such as ammonia nitrogen and the like are further degraded, and 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, the intensified oxidation reaction is continuously carried out, the selective injection of the secondary oxidant or Fenton reagent is selected according to the types and properties of undegraded substances, meanwhile, the liquid-phase product is cooled by the secondary cooling component 17 in the tertiary reaction zone 21, so that the generation of hot walls of the material preheater 7 in the quaternary reaction zone 22 is avoided, the salt deposition of organic materials in the material preheater is caused in the preheating process, the preheater is blocked, and then the liquid-phase product flows into the quaternary reaction zone 22.
In the four-stage reaction zone 22, the liquid-phase product is cooled by the material preheater 7, the organic material in the material preheater 7 is preheated, and then the liquid-phase product flows into the five-stage reaction zone 23.
In the fifth-stage reaction zone 23, the liquid-phase product is subjected to subcritical catalytic oxidation through the catalytic inner lining 4 and the low-temperature catalyst bed 5, and a small amount of small molecular organic matters possibly contained in the liquid-phase product are further thoroughly degraded, so that the product can be discharged after reaching the standard at one time; and the liquid phase product exchanges heat with the three-stage cooling assembly 6 and the wall protection assembly 3, and finally the liquid phase product flows into the reacted fluid collector 13 in a normal temperature and high pressure state and is led out of the reactor, and is directly discharged up to the standard or recycled water is recycled.
In the normal operation process of the reactor, the flow of the cooling water is as follows: entering from a bottom wall temperature control assembly 11 on the bottom seal head 10, and cooling the bottom seal head 10; then sequentially enters the three-stage cooling assembly 6, the wall protection assembly 3, the top wall temperature control assembly 12, the second-stage cooling assembly 17 and the first-stage cooling assembly 13 on the top end cover 1, absorbs the reaction heat generated in the reaction process of the reactor, and finally flows out from the first-stage cooling assembly outlet N6 after heat exchange. The heat exchange components in the reactor can be filled with normal-temperature high-pressure water to generate supercritical water or normal-temperature low-pressure water to generate steam.
In the normal operation process of the reactor, the mechanical scraping device 16 positioned in the primary reaction zone 19 continuously removes inorganic salt deposited on the inner wall surface of the primary cooling component 13, so that the salt deposition on the wall surface is prevented; the inorganic salt is separated from the liquid-phase product under the action of the filter assembly 8, enters the bottom sealing head 10, is dissolved by subcritical water after being further degraded by the oxidant for three times, and is continuously discharged from the salt discharging port N23 on line through the conveying device 18.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The supercritical water reaction device integrating the functions of enhanced oxidation, online desalting and waste heat recovery is characterized by comprising a reactor main body (2) and an end component (1);
the top end of the reactor main body (2) is connected with the end component (1) in a sealing way, and the bottom end of the reactor main body is connected with the bottom seal head (10) in a sealing way; the inner cavity of the reactor main body (2) is a reaction zone and is used for carrying out supercritical water reaction, on-line desalination and salt removal and waste heat recovery; the side wall of the reactor main body (2) is provided with a reacted fluid outlet (N18); a primary cooling assembly (13) is arranged in the reactor main body (2), and a heat insulation sleeve (15) and a catalyst inner bushing (4) are sleeved outside the primary cooling assembly (13) in sequence; the catalyst inner lining (4) is closely attached to the wall surface of the reactor main body (2); the primary cooling component (13) is of a barrel-shaped structure, and the top of the primary cooling component is in sealing connection with the end component (1);
the end component (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 adding port (N9) and a secondary oxidant/Fenton reagent injection port (N10), which are all communicated with a reaction zone of the inner cavity of the reactor main body (2);
the inner cavity of the bottom seal head (10) is a salt discharging area, a tertiary oxidant injection opening (N19) is formed in the side wall of the bottom seal head, and a salt discharging opening (N23) is formed in the bottom of the salt discharging area;
the heat insulation sleeve (15) comprises a first heat insulation cylinder, a second heat insulation cylinder and a third heat insulation cylinder which are sleeved in sequence, the first heat insulation cylinder is sleeved outside the primary cooling assembly (13), a primary reaction zone (19) is arranged inside the primary cooling assembly (13), and a secondary reaction zone (20) is arranged between the inner cavity of the first heat insulation cylinder and the primary cooling assembly (13); the part between the first heat-insulating cylinder and the second heat-insulating cylinder is a three-stage reaction zone (21); the part between the second heat-insulating cylinder and the third heat-insulating cylinder is a four-stage reaction zone (22); the part between the fourth heat insulation cylinder and the catalyst inner lining (4) is a five-stage reaction zone (21);
the bottom of the primary cooling component (12) is provided with a filtering component (8), and the bottom of the primary reaction zone (19) is communicated with a secondary reaction zone (20) through the filtering component (8); the top of the secondary reaction zone (20) is communicated with the tertiary reaction zone (21); the bottom of the third-stage reaction zone (21) is communicated with the fourth-stage reaction zone (22); the top of the four-stage reaction zone (22) is communicated with the five-stage reaction zone (23); the reacted fluid outlet (N18) is communicated with the bottom of the five-stage reaction zone (23);
the device is characterized in that a mechanical scraping device (16) is arranged in the first-stage reaction zone (19), a high-temperature catalyst bed (14) is arranged in the second reaction zone (20), a second-stage cooling component (17) is arranged in the third reaction zone (21), a material preheating component (7) is arranged in the fourth reaction zone (22), and a low-temperature catalyst bed (5), a third-stage cooling component (6) and a post-reaction fluid collector (9) are sequentially arranged in the fifth reaction zone (23) from top to bottom.
2. The supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery according to claim 1, wherein a wall surface protection component (3) is embedded in the wall surface of the reactor main body (2); the wall protection unit (3) is provided with a wall protection unit outlet (N4) and a wall protection unit inlet (N11).
3. The supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery according to claim 1, wherein an end wall temperature control component (12) is embedded in the wall surface of the end component (1).
4. The supercritical water reaction device integrating enhanced oxidation, online desalting and waste heat recovery according to claim 1, wherein a bottom wall temperature control component (11) is arranged on the outer wall surface of the bottom sealing head (10).
5. The supercritical water reaction device for concentrated and enhanced oxidation, online salt removal and waste heat recovery according to claim 1 or 4, wherein a conveying device (18) is arranged at the bottom of a salt removal area of the bottom sealing head (10) and used for conveying reaction products to a salt removal port (N23), and a subcritical water injection port (N22) communicated with a salt removal channel of the conveying device (18) is formed in the side wall of the salt removal port (N23).
6. A supercritical water reaction method for integrated enhanced oxidation, on-line desalination and waste heat recovery by using the device of any one of claims 1-5, comprising the following steps:
when the reactor normally operates, supercritical water/auxiliary fuel enters the reactor from a supercritical water/auxiliary fuel injection port (N1), materials enter the reactor from a material injection port (N2) after being preheated by a material preheating component (7), and oxidant enters the reactor from a primary oxidant injection port (N3); mixing the preheated material with an oxidant, auxiliary fuel/supercritical water and generating a supercritical hydrothermal combustion reaction; the high-temperature and high-pressure reaction product is cooled by a first-stage cooling component (13) in a first-stage reaction zone (19), then filtered by a filtering component (8), the liquid-phase product enters a second-stage reaction zone (20) to continue to react, and the solid-phase product is deposited in a bottom seal head (10);
in the secondary reaction zone (20), the liquid-phase product is catalyzed by a high-temperature catalyst bed layer (14) and a catalyst injected from a catalyst adding port (N9) to continuously perform supercritical water catalytic oxidation reaction, the refractory intermediate product is further degraded, and then the liquid-phase product flows into the tertiary reaction zone (21);
in the third-stage 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) to continue the intensified oxidation reaction; simultaneously, the liquid-phase product is cooled by a secondary cooling assembly (17) in a tertiary reaction zone (21), and then flows into a quaternary reaction zone (22);
in the four-stage reaction zone (22), the liquid-phase product is cooled by a material preheater (7), organic materials in the material preheater (7) are preheated, and then the liquid-phase product flows into a five-stage reaction zone (23);
in a five-stage reaction zone (23), the liquid-phase product is subjected to subcritical catalytic oxidation through a catalytic inner lining (4) and a low-temperature catalyst bed (5), and organic matters in the liquid-phase product are further degraded, so that the product can reach the emission standard; meanwhile, the liquid phase product exchanges heat with the three-stage cooling assembly (6) and the wall protection assembly (3), and finally the liquid phase product flows into the reacted fluid collector (9) in a state of normal temperature and high pressure and is led out of the reactor, and is directly discharged up to standard or recycled water is recycled;
in the normal operation process of the reactor, a mechanical scraping device (16) positioned in a first-stage reaction zone (19) continuously removes inorganic salt deposited on the inner wall surface of a first-stage cooling component (13) to prevent salt deposition on the wall surface; inorganic salt is separated from liquid-phase products under the action of a filtering component (8), enters a bottom sealing head (10), is further degraded by a tertiary oxidant, is dissolved by subcritical water, and is continuously discharged from a salt discharging port (N23) on line through a conveying device (18).
7. The supercritical water reaction method integrating enhanced oxidation, online desalting and waste heat recovery according to claim 6, wherein in the normal operation process of the reactor, the flow of cooling water is as follows:
entering from a bottom wall temperature control assembly (11) on the bottom seal head (10) to cool the bottom seal head (10); then sequentially entering a three-stage cooling assembly (6), a wall protection assembly (3), a top wall temperature control assembly (12), a second-stage cooling assembly (17) and a first-stage cooling assembly (13) on a top end cover (1), absorbing reaction heat generated in the reaction process of the reactor, and finally flowing out cooling water subjected to heat exchange from a first-stage cooling assembly outlet (N6); the heat exchange components in the reactor can be filled with normal-temperature high-pressure water to generate supercritical water or normal-temperature low-pressure water to generate steam.
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