CN114804424A - Supercritical water reaction device integrating enhanced oxidation, online desalting and discharging and waste heat recovery - Google Patents

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

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CN114804424A
CN114804424A CN202210466791.1A CN202210466791A CN114804424A CN 114804424 A CN114804424 A CN 114804424A CN 202210466791 A CN202210466791 A CN 202210466791A CN 114804424 A CN114804424 A CN 114804424A
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reaction zone
reaction
supercritical water
reactor
stage
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CN114804424B (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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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 reinforced oxidation, online desalting and waste heat recovery. The thorough treatment of organic matters is realized by arranging a catalyst bed layer, a catalytic inner liner, a catalyst adding port and a secondary oxidant/Fenton reagent injection port; the removal of inorganic salt is realized on line by arranging a filtering component, a mechanical scraping device, a tertiary oxidant and subcritical water injection port and a conveying device; heat exchangers such as a material preheating assembly, a cooling assembly and a wall surface protection assembly are matched with the heat insulation sleeve, and waste heat recovery of reaction products is achieved inside the reactor. The reaction device realizes the coupling of functions of strengthening oxidation, online desalting and discharging and waste heat recovery, reduces the complexity of the system, improves the economy and 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 desalinization 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 discharge and waste heat recovery.
Background
The supercritical water oxidation technology is a technology capable of realizing deep oxidation treatment on various organic wastes. The principle of supercritical water oxidation technology is supercritical water (T)>374.15℃，P>22.12MPa) as a reaction medium, and the organic matter is quickly converted into CO through homogeneous oxidation reaction by utilizing the excellent organic matter/gas dissolving and transferring performance of the reaction medium 2 、H 2 O、N 2 And S, P and the like are converted into the highest-valence salts for stabilization, so that the heavy metal is mineralized and deposited and then stably exists in the solid-phase residue, and the harmless treatment and resource utilization of the organic waste 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 achieved great success in the aspect of treating various kinds of wastewater and sludge.
When the concentration of organic matter is big enough, the supercritical water oxidation reaction can be more violent, can produce hydrothermal flame even, and this kind of novel combustion mode is called supercritical water heat burning, is a violent oxidation reaction, also is called to have flame supercritical water oxidation, and supercritical water heat burning technology has better prospect in the aspect of handling organic danger.
At present, the reactor among the supercritical water reaction system is mostly tubular reactor or simple kettle formula reactor, and the reactor is as the core among the supercritical water reaction process units, and the upgrading improvement to it is the research and development focus of supercritical water reaction technique always, but still has some problems at present:
(1) the traditional supercritical water reactor generally leads high-temperature fluid after reaction out of the reactor, and then carries out waste heat recovery by using a heat exchanger, so that the defects of complex system, large heat exchange surface, serious corrosion of the wall surface of the reactor due to overhigh temperature and the like exist.
(2) Although the supercritical water oxidation reaction has a good treatment effect on organic hazardous waste, organic matters such as ammonia nitrogen and acetic acid which are refractory intermediate products generated in the reaction process are still difficult to treat, and extremely harsh reaction conditions (high temperature, high pressure and long retention time) are required, so that the investment cost of the system can be remarkably increased, and the economical efficiency of the system is reduced.
(3) Because the solubility of the salts in the supercritical water is low, the salts are easy to crystallize and separate out, salt deposition is caused, the reactor can be blocked in serious cases, the salts can be timely discharged, and the problems that the salt deposition and the blockage are avoided are still further solved.
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 novel reaction apparatus.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a supercritical water reaction device integrating enhanced oxidation, online salt elimination and waste heat recovery.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
collect and strengthen supercritical water reaction unit of oxidation, online desalinization, waste heat recovery, include:
the top end of the reactor main body is connected with the end component in a sealing manner, and the bottom end of the reactor main body is connected with the bottom end enclosure in a sealing manner; the inner cavity of the reactor main body is a reaction area and is used for carrying out supercritical water reaction, online desalination and salt discharge and waste heat recovery; a fluid outlet after reaction is formed in the side wall of the reactor main body;
the end part 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 which are communicated with a reaction zone in the inner cavity of the reactor body;
the inner cavity of the bottom end enclosure is a salt discharge area, a tertiary oxidant injection opening is formed in the side wall of the bottom end enclosure, and a salt discharge opening is formed in the bottom of the salt discharge area.
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 sequentially sleeved outside the primary cooling assembly; the catalyst inner bushing is arranged close to the wall surface of the reactor main body; the first-level cooling assembly is of a barrel-shaped structure, and the top of the first-level cooling assembly is connected with the end assembly in a sealing mode.
A wall surface protection component is embedded in the wall surface of the reactor main body; the wall surface protection component is provided with a wall surface protection component leading-out opening and a wall surface protection component leading-in opening.
The heat insulation sleeve comprises a first heat insulation barrel, a second heat insulation barrel and a third heat insulation barrel which are sequentially sleeved, the first heat insulation barrel is sleeved outside the primary cooling assembly, a primary reaction zone is arranged inside the primary cooling assembly, and a part between the inner cavity of the first heat insulation barrel and the primary cooling assembly is a secondary reaction zone; the part between the first heat insulation cylinder and the second heat insulation 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-insulating cylinder and the catalyst inner bushing is a five-stage reaction zone;
the bottom of the primary cooling assembly is provided with a filtering assembly, and the bottom of the primary reaction zone is communicated with the secondary reaction zone through the filtering assembly; the top of the second-stage reaction zone is communicated with the third-stage reaction zone; the bottom of the third-stage reaction zone is communicated with the fourth-stage reaction zone; the top of the fourth-stage reaction zone is communicated with the fifth-stage reaction zone; the fluid outlet after the reaction is communicated with the bottom of the five-stage reaction area.
The device is characterized in that a mechanical scraping device is arranged in the first-stage reaction zone, a high-temperature catalyst bed layer is arranged in the second reaction zone, a second-stage cooling assembly is arranged in the third reaction zone, a material preheating assembly is arranged in the fourth-stage reaction zone, and a low-temperature catalyst bed layer, a third-stage cooling assembly and a fluid collector after reaction are sequentially arranged in the fifth-stage reaction zone from top to bottom.
An end wall temperature control assembly is embedded in the wall surface of the end assembly.
And a bottom wall surface temperature control assembly is arranged on the outer wall surface of the bottom end enclosure.
And the bottom of the bottom end socket salt discharge area is provided with a conveying device for conveying reaction products to a salt discharge port, and a subcritical water injection port communicated with a salt discharge channel of the conveying device is formed in the side wall of the salt discharge port.
A supercritical water reaction device integrating reinforced oxidation, online desalting and discharging 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 assembly, and an oxidant enters the reactor from a primary oxidant injection port; the preheated materials are mixed with an oxidant and auxiliary fuel/supercritical water and subjected to supercritical water thermal 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 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 end socket;
in the second-stage reaction zone, the liquid-phase product passes through the high-temperature catalyst bed layer and is catalyzed by the catalyst injected from the catalyst addition port to continuously generate 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 a secondary oxidant or a Fenton reagent injected from a secondary oxidant/Fenton reagent injection port, and the enhanced oxidation reaction is continuously carried out; meanwhile, the liquid-phase product is cooled by the secondary cooling component in the third-stage reaction zone, 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 a material preheater, the organic material in the material preheater is preheated, and then the liquid-phase product flows into the fifth-stage reaction zone;
in the five-stage reaction zone, the liquid-phase product is subjected to subcritical catalytic oxidation through the catalytic inner liner 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 standard and be discharged; meanwhile, the liquid phase product exchanges heat with the three-stage cooling assembly and the wall surface protection assembly, and finally the liquid phase product flows into the fluid collector after reaction in a normal-temperature and high-pressure state and is led out of the reactor through the fluid collector to be directly discharged after reaching the standard or recycled;
in the normal operation process of the reactor, a mechanical scraping device positioned in the primary reaction zone continuously removes inorganic salt deposited on the inner wall surface of the primary cooling assembly, so that salt deposition on the wall surface is prevented; inorganic salt is separated from a liquid-phase product under the action of the filtering component, enters the bottom end socket, is further degraded by a tertiary oxidant, is dissolved by subcritical water, and is continuously discharged from the salt discharge port on line through the 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 surface temperature control assembly on the bottom end socket to cool the bottom end socket; then the reaction water sequentially enters a third-stage cooling assembly, a wall surface protection assembly, a top wall surface temperature control assembly on a top end cover, a second-stage cooling assembly and a first-stage cooling assembly, reaction heat generated in the reaction process of the reactor is absorbed, and finally the cooling water after heat exchange flows out from a leading-out port of the first-stage cooling assembly; the heat exchange components in 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.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can realize the coupling of supercritical hydrothermal combustion reaction, high-temperature catalytic oxidation reaction, sectional oxidation, Fenton oxidation, low-temperature catalytic oxidation reaction, wall surface catalytic oxidation and other reactions of the refractory organic waste liquid, and can realize the harmless treatment and standard discharge of the refractory organic waste liquid.
2. The invention utilizes the heat exchange assemblies such as the material preheating assembly, the cooling assembly, the wall surface protection assembly, the wall surface temperature control assembly and the like to be matched with the heat insulation sleeve, realizes the waste heat utilization of high-temperature and high-pressure reaction products in the reactor, reduces the heat exchange loss, and simultaneously realizes the preheating of cold materials.
3. According to the invention, the mechanical desalting device, the filtering component, the tertiary oxidant, the subcritical water injection port and the conveying device are jointly used, so that the continuous online inorganic salt desorption in the reaction process is realized, the corresponding heat is recovered, and the harmlessness and the recycling of the inorganic salt are realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic sectional view of the structure of a reactor according to the present invention.
Wherein, 1-end assembly; 2-a reactor body; 3-a wall protection component; 4-catalytic inner liner; 5-low temperature catalyst bed layer; 6-a three-stage cooling assembly; 7-a material preheating assembly; 8-a filter assembly; 9-post-reaction fluid collector; 10-bottom end enclosure; 11-bottom wall temperature control assembly; 12-end wall temperature control assembly; 13-a primary cooling assembly; 14-high temperature catalyst bed; 15-an insulating sleeve; 16-mechanical scraping means; 17-a secondary cooling assembly; 18-a conveying device; 19-a primary reaction zone; 20-a secondary reaction zone; 21-tertiary reaction zone; 22-quaternary reaction zone; 23-five stage reaction zone; n1-supercritical water/auxiliary fuel injection port; n2-primary oxidant injection port; N3-Material injection opening; n4-wall protection assembly outlet; n5-end wall temperature control assembly inlet; n6-primary cooling module exit; n7-primary cooling module inlet; n8-leading-out port of temperature control component of end wall surface; n9-catalyst addition port; n10-secondary oxidant/fenton reagent injection port; n11-wall protection component lead-in; n12-material preheating component outlet; n13-secondary cooling module exit; n14-tertiary cooling assembly outlet; n15 — secondary cooling module inlet; n16-material preheating assembly inlet; n17-tertiary cooling module inlet; n18-outlet of fluid collector after reaction; n19-tertiary oxidant injection port; n20-bottom wall temperature control assembly outlet; n21-bottom wall temperature control assembly inlet; n22-subcritical water injection port; n23-salt discharge port.
Detailed Description
In order to make the objects, 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 with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of 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 present invention, 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the embodiments of the present invention, it should be noted that, if the terms "upper", "lower", "horizontal", "inner", etc. are used to indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings or the orientation or positional relationship which the product of the present invention is used to usually place, it is only for convenience of describing the present invention and simplifying the description, but it is not necessary to indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to 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. For example, "horizontal" merely means that the 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 be further noted that unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the embodiment of the invention discloses a supercritical water reaction device integrating reinforced oxidation, online salt removal and discharge and waste heat recovery, which comprises a reactor main body 2, an end component 1 and a bottom end enclosure 10.
The top end of the reactor main body 2 is hermetically connected with the end assembly 1, and the bottom end is hermetically connected with the bottom end enclosure 10; the inner cavity of the reactor main body 2 is a reaction area and is used for carrying out supercritical water reaction, online desalination and salt discharge and waste heat recovery; a fluid outlet N18 after reaction is arranged on the side wall of the reactor main body 2; a primary cooling assembly 13 is arranged in the reactor main body 2, and a heat insulation sleeve 15 and a catalyst inner liner 4 are sleeved outside the primary cooling assembly 13 in sequence; the catalyst inner bushing 4 is arranged close to the wall surface of the reactor main body 2; the primary cooling assembly 13 is of a barrel-shaped structure, and the top of the primary cooling assembly is hermetically connected with the end assembly 1. A wall surface protection component 3 is embedded in the wall surface of the reactor main body 2; the wall surface protecting module 3 is provided with a wall surface protecting module outlet N4 and a wall surface protecting module 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 sequentially sleeved, 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 part between the second heat-insulating cylinder and the third heat-insulating cylinder is a four-stage reaction zone 22; a fifth-stage reaction zone 21 is arranged between the fourth heat-insulating cylinder and the catalyst inner bushing 4;
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 the 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 fourth-stage reaction zone 22 is communicated with the fifth-stage reaction zone 23; post-reaction fluid outlet N18 is in communication with the bottom of five-stage reaction zone 23.
A mechanical scraping device 16 is arranged in the first-stage reaction zone 19, a high-temperature catalyst bed layer 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-stage reaction zone 22, and a low-temperature catalyst bed layer 5, a third-stage cooling component 6 and a fluid collector 9 after reaction 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 addition port N9 and a secondary oxidant/Fenton reagent injection port N10 which are communicated with a reaction area of the inner cavity of the reactor main body 2; an end wall temperature control assembly 12 is embedded in the wall of the end assembly 1.
The inner cavity of the bottom end enclosure 10 is a salt discharge area, the side wall of the bottom end enclosure is provided with a tertiary oxidant injection port N19, and the bottom of the salt discharge area is provided with a salt discharge port N23. And a bottom wall surface temperature control assembly 11 is arranged on the outer wall surface of the bottom end enclosure 10. The bottom of the salt discharge area of the bottom end enclosure 10 is provided with a conveying device 18 for conveying a reaction product to a salt discharge port N23, and the side wall of the salt discharge port N23 is provided with a subcritical water injection port N22 communicated with a salt discharge channel of the conveying device 18.
The structural principle of the invention is as follows:
as shown in figure 1, the supercritical water reaction device integrating the functions of strengthening oxidation, online desalting and waste heat recovery comprises an end component 1, a reactor main body 2 and a bottom end enclosure 10; wherein, the end part component 1 is provided with an end part 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 addition 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 bushing 4; the interior 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 insulation sleeve 15 and a first-stage cooling assembly 13; a mechanical scraping device 16 is arranged in the first-stage reaction zone 19, a high-temperature catalyst bed layer 14 is arranged in the second-stage reaction zone 20, a second-stage cooling component 17 is arranged in the third-stage reaction zone 21, a material cooling component 7 is arranged in the fourth-stage reaction zone 22, and a low-temperature catalyst bed layer 5, a third-stage cooling component 6 and a fluid collector 9 after reaction are arranged in the fifth-stage reaction zone 23; the wall surface of the bottom end enclosure 10 is provided with a tertiary oxidant injection port 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 port N22 and a salt discharge port N23.
The end wall surface temperature control component 12 is provided with an inlet N5 and an outlet N8, the wall surface protection component 3 is provided with an inlet N11 and an outlet N4, the material preheating component 7 is provided with an inlet N16 and an outlet N12, the primary cooling component 13 is provided with an inlet N7 and an outlet N6, the secondary cooling component 17 is provided with an inlet N15 and an outlet N13, the tertiary cooling component 6 is provided with an inlet N17 and an outlet N14, the reacted fluid collector 9 is provided with an outlet N18, the bottom wall surface temperature control component 11 is provided with an inlet N21 and an outlet N20, and the inlets and outlets can be arranged on the end component 1, the reactor body 2 or the bottom end enclosure 15.
The inlet and outlet of the bottom wall surface temperature control assembly 11, the third-stage cooling assembly 6, the wall surface protection assembly 3, the end wall surface temperature control assembly 12, the second-stage cooling assembly 17 and the first-stage 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; the forms of these heat exchange assemblies and material preheating assemblies include, but are not limited to, forms of membrane walls, serpentine tubes, coil tubes, water jackets, 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 positions in the secondary reaction zone 20 and the tertiary reaction zone 21, and may be adjusted according to the material properties. The catalytic inner lining 4, the low-temperature catalyst bed 5 and the high-temperature catalyst bed 14 can be detached and replaced.
Mechanical scraping means 16 include, but are not limited to, forms of stirred wipers or the like; the conveying means 18 includes, but is not limited to, a form of a conveying 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 assembly 7, and an oxidant enters the reactor from a primary oxidant injection port N3; the preheated material is mixed with an oxidant and auxiliary fuel/supercritical water and generates supercritical water heat combustion reaction. The high-temperature and high-pressure reaction product is cooled by the primary cooling component 13 in the primary reaction zone 19, then is filtered by the filtering component 8, the liquid-phase product enters the secondary reaction zone 20 to continue to react, and solid-phase products such as salts and the like are deposited in the bottom end enclosure 10;
in the second-stage reaction zone 20, the liquid-phase product passes through the high-temperature catalyst bed layer 14 and is catalyzed by the catalyst injected from the catalyst addition port N9 to continue to generate supercritical water catalytic oxidation reaction, the degradation-resistant intermediate products such as ammonia nitrogen and the like are further degraded, and then the liquid-phase product flows into the third-stage reaction zone 21.
In the third 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 occur, the selective injection of the secondary oxidant or fenton reagent is selected according to the kind and property of the undegraded material, and at the same time, the liquid phase product is cooled by the second cooling assembly 17 in the third reaction zone 21, thereby avoiding the generation of hot wall in the material preheater 7 in the fourth reaction zone 22, causing the organic material in the preheater to be deposited with salt and block the preheater during preheating, 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, 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 five-stage reaction zone 23, the liquid-phase product is subjected to subcritical catalytic oxidation through the catalytic inner liner 4 and the low-temperature catalyst bed layer 5, and a small amount of micromolecular organic matters possibly still contained in the liquid-phase product are further thoroughly degraded, so that the product can be discharged after reaching the standard once; meanwhile, the liquid phase product exchanges heat with the three-stage cooling component 6 and the wall surface protection component 3, and finally the liquid phase product flows into the fluid collector 13 after reaction in a state of normal temperature and high pressure and is led out of the reactor through the fluid collector 13 to be directly discharged after reaching the standard or recycled by using reclaimed water.
In the normal operation process of the reactor, the flow of cooling water is as follows: entering from a bottom wall surface temperature control assembly 11 on the bottom end enclosure 10 to cool the bottom end enclosure 10; and then the reaction product sequentially enters a third-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, reaction heat generated in the reaction process of the reactor is absorbed, and finally cooling water after heat exchange flows out from a first-stage cooling assembly leading-out opening N6. The heat exchange components in 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.
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 assembly 13, so that salt deposition on the wall surface is prevented; inorganic salt is separated from liquid phase products under the action of the filtering component 8, enters the bottom end socket 10, is further degraded by a third oxidant, is dissolved by subcritical water, and is continuously discharged from the salt discharge 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, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. Collect and strengthen supercritical water reaction unit of oxidation, online desalinization, waste heat recovery, its characterized in that includes:
the reactor comprises a reactor main body (2), wherein the top end of the reactor main body (2) is connected with a terminal assembly (1) in a sealing manner, and the bottom end of the reactor main body is connected with a bottom end enclosure (10) in a sealing manner; the inner cavity of the reactor main body (2) is a reaction area and is used for carrying out supercritical water reaction, online desalination and salt discharge and waste heat recovery; a fluid outlet (N18) after reaction is arranged on the side wall of the reactor main body (2);
the reactor comprises an end component (1), wherein 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 addition port (N9) and a secondary oxidant/Fenton reagent injection port (N10), which are communicated with a reaction area of an inner cavity of a reactor main body (2);
the bottom end enclosure (10), the inner chamber of bottom end enclosure (10) is row salt district, sets up cubic oxidant injection mouth (N19) on the lateral wall, arranges the bottom in salt district and sets up row salt mouth (N23).
2. The supercritical water reaction device with the functions of strengthening oxidation, online desalting and waste heat recovery as claimed in claim 1, wherein a primary cooling assembly (13) is arranged in the reactor body (2), and a heat insulation sleeve (15) and a catalyst inner bushing (4) are sequentially sleeved outside the primary cooling assembly (13); the catalyst inner bushing (4) is arranged close to the wall surface of the reactor main body (2); the primary cooling assembly (13) is of a barrel-shaped structure, and the top of the primary cooling assembly is hermetically connected with the end assembly (1).
3. The supercritical water reaction apparatus with integrated reinforced oxidation, online salt elimination and waste heat recovery according to claim 1 or 2 is characterized in that a wall surface protection component (3) is embedded in the wall surface of the reactor main body (2); the wall surface protection component (3) is provided with a wall surface protection component outlet (N4) and a wall surface protection component inlet (N11).
4. The supercritical water reaction device with the functions of strengthening oxidation, online desalting and waste heat recovery as claimed in claim 2, wherein the heat-insulating sleeve (15) comprises a first heat-insulating cylinder, a second heat-insulating cylinder and a third heat-insulating cylinder which are sequentially sleeved, the first heat-insulating cylinder is sleeved outside the primary cooling assembly (13), the primary cooling assembly (13) is internally provided with a primary reaction zone (19), and the part between the inner cavity of the first heat-insulating cylinder and the primary cooling assembly (13) is a secondary reaction zone (20); 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); a fifth-stage reaction zone (21) is arranged between the fourth heat-insulating cylinder and the catalyst inner bushing (4);
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 the 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 fourth-stage reaction zone (22) is communicated with the fifth-stage reaction zone (23); the reacted fluid outlet (N18) is communicated with the bottom of the five-stage reaction zone (23).
5. The supercritical water reaction device with the functions of strengthening oxidation, online desalting and waste heat recovery as claimed in claim 4, wherein 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-stage reaction zone (22), and a low-temperature catalyst bed (5), a third-stage cooling component (6) and a fluid collector (9) after reaction are sequentially arranged in the fifth-stage reaction zone (23) from top to bottom.
6. The supercritical water reaction apparatus with integrated reinforced oxidation, online salt elimination and waste heat recovery according to claim 1 or 2 is characterized in that an end wall temperature control component (12) is embedded in the wall surface of the end component (1).
7. The supercritical water reaction device with integrated functions of enhanced oxidation, online salt elimination and waste heat recovery according to claim 1, wherein a bottom wall temperature control assembly (11) is arranged on the outer wall surface of the bottom head (10).
8. The supercritical water reaction apparatus integrating enhanced oxidation, online desalination and waste heat recovery as claimed in claim 1 or 7, wherein the bottom of the salt discharge area of the bottom head (10) is provided with a conveying device (18) for conveying reaction products to a salt discharge port (N23), and the side wall of the salt discharge port (N23) is provided with a subcritical water injection port (N22) communicated with the salt discharge channel of the conveying device (18).
9. A supercritical water reaction method integrating enhanced oxidation, online salt elimination and waste heat recovery by adopting the device of any one of claims 1 to 8, which is characterized by 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 assembly (7), and an oxidant enters the reactor from a primary oxidant injection port (N3); the preheated materials are mixed with an oxidant and auxiliary fuel/supercritical water and subjected to supercritical water thermal combustion reaction; the high-temperature and high-pressure reaction product is cooled by a primary cooling component (13) in a primary reaction zone (19), then is filtered by a filtering component (8), a liquid-phase product enters a secondary reaction zone (20) to continue to react, and a solid-phase product is deposited in a bottom end socket (10);
in the secondary reaction zone (20), the liquid phase product passes through the high-temperature catalyst bed layer (14) and is catalyzed by the catalyst injected from the catalyst adding port (N9) to continue to generate 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 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) to continue to generate the enhanced oxidation reaction; meanwhile, the liquid phase product is cooled by a secondary cooling component (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 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 five-stage reaction zone (23), the liquid-phase product is subjected to subcritical catalytic oxidation through the catalytic inner bushing (4) and the low-temperature catalyst bed layer (5), and organic matters in the liquid-phase product are further degraded, so that the product can reach the standard and be discharged; meanwhile, the liquid phase product exchanges heat with the three-stage cooling assembly (6) and the wall surface protection assembly (3), and finally the liquid phase product flows into the fluid collector (13) after reaction in a state of normal temperature and high pressure and is led out of the reactor through the fluid collector to be directly discharged after reaching the standard or recycled;
in the normal operation process of the reactor, a 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) to prevent the salt deposition on the wall surface; inorganic salt is separated from a liquid phase product under the action of the filtering component (8), enters the bottom end enclosure (10), is further degraded by a third oxidant, is dissolved by subcritical water, and is continuously discharged from the salt discharge port (N23) on line through the conveying device (18).
10. The supercritical water reaction method integrating enhanced oxidation, online desalination and waste heat recovery according to claim 9, wherein in the normal operation of the reactor, the flow of cooling water is as follows:
entering from a bottom wall surface temperature control assembly (11) on the bottom end enclosure (10) to cool the bottom end enclosure (10); then the reaction product sequentially enters a third-stage cooling assembly (6), a wall protection assembly (3), a top wall temperature control assembly (12) on a top end cover (1), a second-stage cooling assembly (17) and a first-stage cooling assembly (13), reaction heat generated in the reaction process of the reactor is absorbed, and finally cooling water after heat exchange flows out from a first-stage cooling assembly lead-out port (N6); the heat exchange components in 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115259340A (en) * 2022-08-26 2022-11-01 北京新风航天装备有限公司 Salt discharging device for supercritical water oxidation system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168771B1 (en) * 1997-02-19 2001-01-02 Hitachi, Ltd. Supercritical oxidation process and apparatus
JP2001300289A (en) * 2000-04-19 2001-10-30 Mitsubishi Materials Corp Reaction treatment apparatus by supercritical water
CN111762866A (en) * 2020-06-26 2020-10-13 西安交通大学 Multifunctional supercritical water enhanced oxidation system for refractory nitrogenous and high-salinity organic pollutants
CN214571322U (en) * 2021-01-20 2021-11-02 贵州航天朝阳科技有限责任公司 Supercritical water oxidation reaction device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168771B1 (en) * 1997-02-19 2001-01-02 Hitachi, Ltd. Supercritical oxidation process and apparatus
JP2001300289A (en) * 2000-04-19 2001-10-30 Mitsubishi Materials Corp Reaction treatment apparatus by supercritical water
CN111762866A (en) * 2020-06-26 2020-10-13 西安交通大学 Multifunctional supercritical water enhanced oxidation system for refractory nitrogenous and high-salinity organic pollutants
CN214571322U (en) * 2021-01-20 2021-11-02 贵州航天朝阳科技有限责任公司 Supercritical water oxidation reaction device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115259340A (en) * 2022-08-26 2022-11-01 北京新风航天装备有限公司 Salt discharging device for supercritical water oxidation system

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