A solid precipitation device and a solid precipitation method

Abstract

A solid precipitation device comprising a device housing (5), a wastewater inlet (1), a discharge outlet (10) and a solid particle (4) arranged in the interior of the device housing (5), wherein the solid particle (4) is configured to deposit and load solid matter thereon, the interior of the device housing (5) further comprising an inner member, a guiding structure (7) arranged around the inner wall of the device housing (5), a heat agent inlet and an inner cylinder (12), the inner member comprising a hollow cylinder (8) substantially coaxial with the central axis of the device housing (5), a canopy (9) arranged above the hollow cylinder (8), the guiding structure (7) arranged in the upper portion of the interior of the device housing (5) and the inner cylinder (12) arranged below the guiding structure (7). A method for solid precipitation is also disclosed, wherein a material containing solute enters the solid precipitation device and at least a portion of the solute is deposited and loaded on the solid particle (4) in the solid precipitation device.

Description

TECHNICAL FIELD

[0001] The present application relates to a solid precipitation device, in particular a desalination device for high-salinity wastewater. The present application also relates to a method for solid precipitation using the solid precipitation device. BACKGROUND

[0002] High-salinity wastewater refers to wastewater with a total salt content of at least 1%. The wastewater discharged from some industrial sectors, such as oil exploration, printing and dyeing, papermaking, pharmaceuticals and chemical industry, generally contains about 15%-25% of salt. Such wastewater contains various substances (including salt, oil, organic matter, heavy metals and radioactive substances), and if directly discharged without treatment, it will inevitably cause great harm to water organisms, drinking water and water for industrial and agricultural production.

[0003] At present, the research on high-salinity wastewater at home and abroad mainly includes biological methods and physical and chemical methods. The biological method shows a high organic matter removal rate when treating high-salinity wastewater, but high-concentration salt substances have an inhibitory effect on microorganisms, and the salt content of the influent needs to be controlled. The physical and chemical methods mainly include evaporation, electrochemical method, ion exchange method and membrane separation technology, but all have problems such as large investment, high operation cost and easy secondary pollution of regenerated wastewater, and it is difficult to achieve the expected purification effect.

[0004] CN105461134A discloses a process and device for salt resourceization of coal chemical high-salinity wastewater, which recovers water, sodium chloride and sodium sulfate in industrial wastewater through three units of nanofiltration salt separation, double-in double-out multi-effect evaporation and aging mother liquor treatment.

[0005] CN104326615A discloses an energy-saving high-salinity wastewater treatment system and a treatment method thereof. The system includes a forward osmosis salt concentration device and a multi-effect evaporator. The forward osmosis salt concentration device includes a F0 membrane closed exchange box, a draw solution recycling device and a clean water recovery device. The F0 membrane closed exchange box is provided with at least one stage. The draw solution recycling device is connected with each F0 membrane closed exchange box through an electric valve. The clean water recovery device is connected with the draw solution recycling device. Each F0 membrane closed exchange box is connected in sequence through a liquid discharge electric valve, and is connected with a mother liquor multi-effect evaporator through a bypass electric valve.

[0006] CN105110542A discloses a zero-emission salt separation and purification method for industrial high-salinity wastewater. The method first recovers sodium sulfate in concentrated brine through a freezing method. The effluent is further concentrated to 25-30% by an evaporator, and then enters a forced circulation crystallizer. When the solid content in the crystallizer reaches 30-35%, the crystallizer is discharged by a circulating pump to a hydrocyclone to realize preliminary solid-liquid separation. The crystalline containing a small amount of mother liquor is separated by a centrifuge to realize complete solid-liquid separation. The mother liquor separated by the centrifuge is directly discharged to a mother liquor tank. SUMMARY

[0007] The inventors of the present application have found, through intensive research, a solid precipitation device and a solid precipitation method, which can meet the need for long-period stable operation and achieve efficient removal of salt from wastewater, particularly when used for desalination of high-salinity wastewater, and solve the problems of difficulty in desalination of high-salinity wastewater and easy clogging.

[0008] Specifically, the present application relates to the following aspects:

[0009] 1. A solid precipitation device (particularly a desalination device) comprising a housing (such as a vertical housing, particularly a vertical cylindrical housing), a material (such as a solution, seawater or wastewater, particularly salt-containing wastewater or high-salinity wastewater, which comprises a solvent and a solute) inlet, a discharge outlet (i.e. a material outlet) and a carrier disposed in the inner cavity of the housing, wherein the carrier is configured to be suitable for deposition and loading of solid substances thereon.

[0010] 2. The solid precipitation device according to any one of the preceding or subsequent aspects, which is operated under supercritical conditions (particularly under supercritical conditions of the solvent such as water).

[0011] 3. The solid precipitation device according to any one of the preceding or subsequent aspects, wherein the carrier is at least one selected from the group consisting of solid particles (such as at least one selected from the group consisting of seeds, inorganic particles such as alumina balls, silica balls, sand, quartz sand, ceramic particles, and solid waste such as slag), plates (such as non-porous plates and porous plates), grids, meshes, cages, fibers and strips, preferably solid particles.

[0012] 4. The method according to any one of the preceding or subsequent aspects, wherein the amount (by volume) of the solid particles is 1 / 4-3 / 4 (preferably 1 / 4-1 / 2) of the total volume of the inner cavity of the housing, and / or the equivalent diameter of the solid particles is 0.1-1.0 mm (preferably 0.2-0.7 mm), and / or the specific surface area of the solid particles is 100-300 m 2 / g, and / or the bulk density of the solid particles is 0.6-0.7 g / cm 3 .

[0013] 5. The solid precipitation device according to any one of the preceding or following aspects, further comprising an inner member arranged in the inner cavity of the housing, in particular in the upper portion, wherein the inner member comprises a hollow cylinder which is substantially coaxial with the central axis of the housing, the hollow cylinder having an open upper end and an open lower end, the hollow cylinder comprising a straight cylinder section in the upper portion and a conical diffuser section in the lower portion, a gap (referred to as a first gap, in particular a ring-shaped gap) being present between the inner wall of the housing and the outer wall of the hollow cylinder, the inner member further comprising a baffle (such as a baffle umbrella) arranged above the hollow cylinder, the baffle umbrella being preferably substantially coaxial with the central axis of the housing, a gap (referred to as a second gap, in particular a ring-shaped gap) being present between the upper edge of the hollow cylinder and the baffle umbrella, and a gap (referred to as a sixth gap, in particular a ring-shaped gap) being present between the inner wall of the housing and the baffle umbrella.

[0014] 6. The solid precipitation device according to any one of the preceding or following aspects, wherein the baffle umbrella is coaxial with the hollow cylinder, the cone angle being in the range of 30-150° (preferably 60-120°), and / or the outer diameter of the straight cylinder section of the hollow cylinder is in the range of 60-80% (preferably 67-73%) of the inner diameter of the housing, and / or the height of the straight cylinder section of the hollow cylinder is in the range of 10-30% of the height of the inner cavity of the housing, and / or the maximum outer diameter of the conical diffuser section of the hollow cylinder is in the range of 75-90% of the inner diameter of the housing, and / or the height of the conical diffuser section of the hollow cylinder is in the range of 3-10% of the height of the inner cavity of the housing, and / or the height of the baffle umbrella is in the range of 5-20% of the height of the inner cavity of the housing.

[0015] 7. The solid precipitation device according to any one of the preceding or following aspects, further comprising a guiding structure arranged around the inner wall of the housing, preferably having a trapezoidal shape in a longitudinal section along the central axis of the housing, the trapezoidal shape having an acute angle a and an acute angle β (preferably in the range of 5-70°), the guiding structure forming a passage (in particular a cylindrical passage, referred to as a guiding opening) which is open at the upper end and at the lower end of the inner cavity of the housing, the guiding structure being arranged below the hollow cylinder and above the material inlet, a gap (referred to as a third gap, in particular a ring-shaped gap) being present between the lower edge of the hollow cylinder and the guiding structure, and / or the guiding opening being substantially coaxial with the central axis of the housing, and / or the guiding structure being arranged in the upper portion of the inner cavity of the housing.

[0016] 8. The solid precipitation device according to any of the preceding or following aspects, wherein the material inlet is located at the bottom or lower part of the housing, the material inlet is structured to spray the material into the interior of the housing (the material inlet is preferably a nozzle or a liquid distributor), and / or, the material outlet is located at the top or upper part of the housing (preferably above the baffle), and / or, the ratio of the height of the interior of the housing (in m) to the inner diameter of the housing (in m) is 7-17, preferably 10-14, and / or, the inner diameter of the guiding opening is 60-80% of the inner diameter of the housing, and / or, the height of the guiding opening is 5-15% of the height of the interior of the housing.

[0017] 9. The solid precipitation device according to any of the preceding or following aspects, further comprising a carrier inlet and a carrier outlet, and / or, the carrier inlet is located at the top or upper part of the housing (preferably above the guiding structure, more preferably above the baffle), and / or, the carrier outlet is located at the bottom of the housing (preferably below the material inlet).

[0018] 10. The solid precipitation device according to any of the preceding or following aspects, further comprising a heat agent inlet, the heat agent inlet is located at the bottom or lower part of the housing, the heat agent inlet is structured to spray a heat agent (such as air, oxygen or a heating gas) into the interior of the housing (the heat agent inlet is preferably a nozzle or a gas distributor), and / or, the heat agent inlet is located above or below the material inlet (preferably below the material inlet).

[0019] 11. The solid precipitation apparatus of any of the preceding or following aspects, further comprising an inner cylinder (such as a straight or trumpet cylinder, in particular a straight circular cylinder, which is preferably substantially coaxial with the central axis of the housing), the hot agent inlet is located at the bottom of the housing, there is a gap (referred to as the fourth gap, in particular an annular gap) between the inner wall of the housing and the outer wall of the inner cylinder, there is a gap (referred to as the fifth gap, in particular an annular gap) between the lower edge or inner wall of the inner cylinder and the hot agent inlet, the fifth gap communicates the fourth gap with the inner space of the inner cylinder, the inner cylinder is configured such that substantially all of the hot agent input from the hot agent inlet enters the inner space of the inner cylinder, the material inlet is arranged in the fourth gap and below the upper edge of the inner cylinder, and / or, referring to the inner cavity space of the housing below the upper edge of the inner cylinder as the buffer zone, the buffer zone accounts for 25-40% or 20-60% of the total volume of the inner cavity of the housing, and / or, the hot agent inlet is a gas distributor (which is preferably substantially coaxial with the central axis of the housing), and the inner cylinder is located above or contains the gas distributor, separated by the fifth gap, and / or, the inner cylinder is located below the guide structure, and / or, the material inlet is 100-500 mm lower than the upper edge of the inner cylinder in the vertical direction, and / or, the outer diameter of the inner cylinder is 60-80% (preferably 67-73%) of the inner diameter of the housing, and / or, the height of the inner cylinder is 20-60% (preferably 30-50%) of the height of the inner cavity of the housing, and / or, the inner cylinder is arranged in the lower part of the inner cavity of the housing.

[0020] 12. A solid precipitation method (in particular a desalination method), comprising introducing a material comprising a solute (such as an inorganic salt) and a solvent (such as water) into the solid precipitation apparatus of any of the preceding or following aspects, causing at least a portion of the solute to precipitate (such as due to a precipitation reaction or due to supersaturation) and load on the carrier arranged in the inner cavity of the housing.

[0021] 13. The solid precipitation method of any preceding or subsequent aspect, wherein the material is maintained in a subcritical state (in particular at a temperature below the supercritical temperature of the solvent, such as ambient temperature to a temperature 1-15°C, 4-10°C or 6-8°C below the supercritical temperature of the solvent (in particular water), and more particularly at or above the supercritical pressure of the solvent but below the supercritical temperature of the solvent, such as ambient temperature to a temperature 1-15°C, 4-10°C or 6-8°C below the supercritical temperature of the solvent (in particular water)) prior to entry into the solid precipitation device, and / or the temperature of the carrier is above the supercritical temperature of the solvent (such as a temperature 1-15°C, 4-10°C or 6-8°C above the supercritical temperature), and / or the carrier is added to the housing lumen and the temperature of the carrier is above the supercritical temperature of the solvent (such as a temperature 1-15°C, 4-10°C or 6-8°C above the supercritical temperature), and / or the ratio of carrier to material is such that the temperature of the material reaches or exceeds the supercritical temperature of the solvent upon mixing.

[0022] 14. The solid precipitation method of any preceding or subsequent aspect, wherein the operating conditions of the housing lumen include an operating pressure of 23-35 MPaG (preferably 25-30 MPaG), an operating temperature of 350-650°C (preferably 380-650°C, 450-600°C or 450-550°C), a residence time of 10-1800 seconds (preferably 60-600 seconds), and an airspeed of 1.5-270 h -1 .

[0023] 15. The solid precipitation method of any preceding or subsequent aspect, wherein a heat agent is added to the housing lumen and the heat agent is used in an amount such that the material forms a supercritical state (such as reaches or exceeds the supercritical temperature of the solvent) upon entry into the housing lumen, and / or the material is a salt-containing or high-salt wastewater (in particular a high-salt organic wastewater), the heat agent is an oxidising gas (such as oxygen or air), and / or the ratio of heat agent to material is such that the temperature of the material reaches or exceeds the supercritical temperature of the solvent upon mixing, and / or the ratio of heat agent to material is such that the temperature of the material reaches or exceeds the supercritical temperature of the solvent upon exiting the upper extent of the inner cylinder, and / or the heat agent is used in an amount of 100-500%, preferably 150-350%, of the theoretical oxygen demand of the material.

[0024] 16. The solid precipitation method of any preceding or subsequent aspect, wherein a pH adjuster is added to the material and / or to the housing lumen and the pH adjuster is used in an amount such that the pH of the contents of the housing lumen is maintained at 9-13.

[0025] 17. The solid precipitation process of any preceding or following aspect, wherein the material enters the lower portion of the housing interior from the material inlet, the carrier enters the upper portion of the housing interior from the carrier inlet, then passes through the first gap, the third gap, and the guide port into the lower portion of the housing interior, the material renders the carrier in a flowable state, at least a portion of the solute deposits and loads onto the carrier to form a loaded carrier, a portion of the loaded carrier moves toward the bottom of the housing interior, exits the housing interior from the carrier exit port, another portion of the loaded carrier moves with the material from which at least a portion of the solute has been removed (referred to as purified material) toward the upper portion of the housing interior, passes through the guide port, enters the straight section from the conical diffuser section, then exits from the second gap, the loaded carrier returns to the lower portion of the housing interior via the first gap, the third gap, and the guide port, the purified material moves toward the top of the housing interior via the sixth gap, and exits the housing interior from the material exit port.

[0026] or,

[0027] the carrier enters the upper portion of the housing interior from the carrier inlet, then passes through the first gap, the third gap, and the guide port into the lower portion of the housing interior,

[0028] the material enters the fourth gap from the material inlet, then passes through the fifth gap into the interior space of the inner cylinder, mixes with the heating agent that enters the interior space of the inner cylinder from the heating agent inlet to form a mixture, and exits the inner cylinder from the upper edge of the inner cylinder after the temperature of the mixture increases to reach or exceed the supercritical temperature of the solvent,

[0029] a portion of the mixture returns to the interior space of the inner cylinder via the fourth gap and the fifth gap (forming an internal circulation), another portion of the mixture renders the carrier in a flowable state, at least a portion of the solute deposits and loads onto the carrier to form a loaded carrier, a portion of the loaded carrier moves toward the bottom of the housing interior via the fourth gap, exits the housing interior from the carrier exit port, another portion of the loaded carrier moves with the mixture from which at least a portion of the solute has been removed (referred to as purified mixture) toward the upper portion of the housing interior, passes through the guide port, enters the straight section from the conical diffuser section, then exits from the second gap, the loaded carrier returns to the lower portion of the housing interior via the first gap, the third gap, and the guide port, the purified mixture moves toward the top of the housing interior via the sixth gap, and exits the housing interior from the material exit port.

[0030] 18. The solid precipitation method of any of the preceding or following aspects, wherein the material is high-salinity wastewater (particularly high-salinity organic wastewater), the TDS of the high-salinity wastewater is not higher than 20 wt% (preferably 5-20 wt%), and the COD is greater than 20000 mg / L (preferably 20000-200000 mg / L or 20000-40000 mg / L).

[0031] In another aspect, the present application relates to the following aspects:

[0032] 1. A method for treating high-salinity organic wastewater, characterized in that it comprises the following steps: feeding high-salinity organic wastewater and an oxidizing agent into a boiling bed reactor, and performing a reaction under supercritical water oxidation conditions, so that the salts in the wastewater are deposited onto the solid particles in the boiling bed reactor; and after the reaction, performing gas-liquid separation on the material, so that the material meets the discharge requirements.

[0033] 2. The method of any of the preceding or following aspects, wherein the COD of the high-salinity organic wastewater is as high as tens of thousands of mg / L to hundreds of thousands of mg / L, preferably 20000-200000 mg / L, and the TDS is not higher than 20 wt%, preferably 5 wt%-20 wt%.

[0034] 3. The method of any of the preceding or following aspects, wherein the oxidizing agent is at least one of air and oxygen, and the amount of the oxidizing agent is 100%-500% of the theoretical oxygen demand for the oxidation of the wastewater, preferably 150%-350%.

[0035] 4. The method of any of the preceding or following aspects, wherein the solid particles in the boiling bed reactor are at least one of alumina ceramic beads and silica beads.

[0036] 5. The method of any of the preceding or following aspects, wherein the diameter of the solid particles is 0.1-1.0 mm, preferably 0.2-0.7 mm, the specific surface area of the solid particles is 100-300 m 2 / g, and the bulk density of the solid particles is 0.6-0.7 g / cm 3 .

[0037] 6. The method of any of the preceding or following aspects, wherein the amount of the solid particles added is 1 / 4-3 / 4 of the volume of the reactor.

[0038] 7. The method of any of the preceding or following aspects, wherein the boiling bed reactor is provided with an online solid particle adding and discharging system, and the solid particles in the boiling bed reactor are periodically added and discharged.

[0039] 8. The method according to any of the preceding or subsequent aspects, characterized in that the discharged salt-containing solid particles are used to recover the salt deposited on the particulate matter by ultrasonic, high-temperature stirring or grinding, thereby regenerating the particulate matter.

[0040] 9. The method according to any of the preceding or subsequent aspects, characterized in that the supercritical water oxidation is operated at a pressure of 23-30 MPa and a temperature of 380-650°C, preferably 450-600°C, and for a time period of 10-180 seconds.

[0041] 10. The method according to any of the preceding or subsequent aspects, characterized in that the material after the supercritical water oxidation is introduced into a gas-liquid separation tank, and the liquid phase is discharged after being heat-exchanged with the feed wastewater of the reactor, or the feed wastewater is diluted to keep the COD content of the material entering the supercritical water oxidation reactor stable, thereby keeping the reaction stable and avoiding large fluctuations in the temperature in the reactor.

[0042] 11. The method according to any of the preceding or subsequent aspects, characterized in that an appropriate amount of alkali solution is added to the feed wastewater to control the pH of the feed water to be 9-13.

[0043] 12. The method according to any of the preceding or subsequent aspects, characterized in that the alkali solution is at least one of sodium hydroxide and potassium hydroxide solution.

[0044] Technical effects

[0045] The present application can achieve at least one of the following technical effects:

[0046] (1) The solid precipitation device and method, in particular the desalination device and method, according to the present application are easy to operate, can meet the needs of long-period (such as continuous operation for more than 20 days, preferably more than 30 days, more than 50 days or more than 100 days) stable operation, can achieve efficient removal of salt from wastewater, and solve the problems of difficulty in desalination of high-salinity wastewater and easy deposition or blockage in the device and pipeline.

[0047] (2) The solid precipitation device and method, in particular the desalination device and method, according to the present application, by having specific internal components, ensure efficient separation of solid particles and desalted material, avoid large amounts of solid particles from being carried out, and at the same time can ensure long-period (such as continuous operation for more than 20 days, preferably more than 30 days, more than 50 days or more than 100 days) stable operation.

[0048] (3) According to the solid precipitation device and method, especially the desalination device and method, by setting the buffer zone, the reaction temperature is raised by the oxidation heat release of the organic matter in the wastewater, the control of the salt precipitation area is realized, the decomposition and removal of the organic matter can be achieved, and the deposition and blockage at the bottom of the desalination device are avoided, so that the two effects are achieved at one time.

[0049] (4) According to a preferred embodiment of the present application, the ebullated bed reactor is combined with the supercritical water oxidation technology to treat the high-salt organic wastewater. After treatment, the desalination rate of the wastewater is higher than 95%, the COD removal rate can reach more than 99%, and the effluent COD is less than 60 mg / L, which meets the direct discharge requirements. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 Flow chart of an embodiment of the desalination method of the present application.

[0051] Wherein: 1-heat exchanger, 2-ebullated bed reactor, 3-gas-liquid separation tank, 4-solid particle online adding system, 5-solid particle online discharging system.

[0052] Figure 2 Structure schematic diagram of an embodiment of the desalination device of the present application.

[0053] Wherein: 1-wastewater inlet, 2-solid particle discharge outlet, 3-liquid distributor, 4-solid particle, 5-device shell, 6-guiding port, 7-guiding structure, 8-hollow cylinder, 9-umbrella, 10-discharge port, 11-solid particle adding port.

[0054] Figure 3 Structure schematic diagram of another embodiment of the desalination device of the present application.

[0055] Wherein: 1-gas inlet, 2-solid particle discharge outlet, 3-gas distributor, 4-solid particle, 5-device shell, 6-guiding port, 7-guiding structure, 8-hollow cylinder, 9-umbrella, 10-discharge port, 11-solid particle adding port, 12-inner cylinder, 13-1, 2-wastewater inlet.

[0056] Figure 4 Structure schematic diagram of another embodiment of the desalination device of the present application.

[0057] Wherein: 1-gas inlet, 2-solid particle discharge outlet, 3-gas distributor, 4-inner cylinder, 5-1, 2-wastewater inlet, 6-device shell, 7-hollow cylinder, 8-umbrella, 9-discharge port, 10-solid particle adding port. DETAILED DESCRIPTION

[0058] The specific embodiments of the present application are explained hereinafter in detail, but it should be noted that the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims attached hereto.

[0059] All publications, patent applications, patents and other references mentioned in this specification are herein incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification are intended to have the meanings commonly attributed to them by those of ordinary skill in the art. In case of conflict between the definitions in this specification and those of any incorporated reference, the definition in this specification will control.

[0060] When the specification uses phrases such as “known to those skilled in the art”, “prior art”, or similar phrases to introduce material, substances, methods, steps, devices or components, etc., the objects introduced by these phrases encompass those that are conventionally used at the time of filing of this application, but also include those that are not yet conventionally used, but will become recognized as suitable for similar purposes in the art.

[0061] In the context of this specification, the term “substantially” means that a deviation that is acceptable or considered reasonable by those skilled in the art is allowed, such as a deviation within ±10%, within ±5%, within ±1%, within ±0.5%, or within ±0.1%.

[0062] In the context of this specification, room temperature means 25°C.

[0063] In the context of this specification, COD is determined using the analysis method provided in HJ828-2017, TDS is determined using the analysis method provided in HJT51-1999, and bulk density is determined using the analysis method provided in GB / T6286-1986.

[0064] In the context of this specification, the size and shape of various gaps (such as the first gap to the sixth gap described hereinafter in this specification) are not particularly limited, as long as they can function as a communication channel and allow various streams (such as the material, carrier, loaded carrier, thermal agent, etc. described hereinafter in this specification) to flow therethrough.

[0065] In the absence of explicit indications, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, and the pressure is gauge pressure.

[0066] In the context of this specification, any two or more embodiments of the present application can be combined arbitrarily, and the technical solutions formed thereby are part of the original disclosure of this specification and also fall within the scope of protection of the present application.

[0067] According to one embodiment of the present application, it relates to a solid precipitation device. Here, as the solid precipitation device, specifically, for example, any device applicable to a case where at least a part of solute in a material including a solvent and solute is precipitated in a solid form due to a physical change (such as a decrease in solubility to form a precipitate) can be cited, more specifically, for example, a desalination device and a crystallization device, particularly a desalination device. In the context of the present specification, the solid precipitation device of the present application is explained and described in detail mainly with the desalination device as an example, but the present application is obviously not limited to the desalination device.

[0068] According to one embodiment of the present application, as the material, specifically, for example, a solution, seawater, or wastewater, particularly salt-containing wastewater or high-salt wastewater, particularly high-salt organic wastewater (also referred to as high-salt organic wastewater) can be cited. However, the present application is not limited to these specific materials, and any material including a solvent and solute and desiring at least a part of the solute contained therein to be precipitated in a solid form as described above in the context of the present specification is applicable to the present application. Here, as the high-salt wastewater, its TDS is generally not higher than 20 wt%, preferably 5-20 wt%. In the case of containing organic matter, the COD of the high-salt wastewater is generally greater than 20000 mg / L, preferably 20000-200000 mg / L or 20000-40000 mg / L.

[0069] According to one embodiment of the present application, the material is maintained in a subcritical state before entering the solid precipitation device, particularly below the supercritical temperature of the solvent, more particularly at or above the supercritical pressure of the solvent (such as 23-35 MPaG, preferably 25-30 MPaG) but below the supercritical temperature of the solvent. Here, as the temperature of the material, for example, any temperature lower than the supercritical temperature of the solvent, particularly room temperature to a temperature 1-15°C, 4-10°C, or 6-8°C lower than the supercritical temperature of the solvent (particularly water) can be cited.

[0070] According to one embodiment of the present application, the solid precipitation device includes a housing (i.e., a device housing), a material inlet, a discharge port (i.e., a material outlet), and a carrier provided in the inner cavity of the housing.

[0071] According to one embodiment of the present application, as the housing, specifically, for example, a vertical housing, particularly a vertical cylindrical housing can be cited.

[0072] According to one embodiment of the present application, the ratio of the inner cavity height (unit: m) to the inner diameter (unit: m) of the housing is 7-17, preferably 10-14.

[0073] According to one embodiment of the present application, the carrier is configured to be suitable for deposition and loading of solid substances (such as various precipitates as described above) thereon, thereby forming a core-shell structure (also referred to as a loaded carrier) with the precipitates as the shell and the carrier as the core. When the loaded carrier grows to a predetermined size (i.e., the carrier is loaded with a predetermined amount of the precipitates), it can be removed or discharged from the solid precipitation device as appropriate, while a new carrier is simultaneously or subsequently replaced to continue the solid precipitation process. Here, as the carrier, any structure and shape that can achieve the purpose can be used, such as, for example, solid particles, plates, grids, nets, cages, fibers, and bars, and preferably solid particles.

[0074] In the context of the present specification, the phrase "the carrier is configured to be suitable for deposition and loading of solid substances thereon" means that the shape or structure of the carrier is designed to specifically or intentionally allow deposition and loading of a large amount of solid substances (such as 80 wt% or more, 90 wt% or more, 95 wt% or more, or 98 wt% or more of the total amount of solid substances) thereon.

[0075] According to one embodiment of the present application, as the solid particles, for example, seed crystals such as inorganic salt particles can be used, which are particularly suitable for desalination or crystallization; inorganic particles, particularly refractory particles, such as alumina balls, silica balls, sand, quartz sand, and ceramsite, which are particularly suitable for desalination using the inorganic particles as intermediates; and solid waste, such as slag and solid garbage, which is particularly suitable for waste recycling.

[0076] According to one embodiment of the present application, in order to achieve optimal deposition and loading, the solid particles are brought into contact with the material in the solid precipitation device to form a fluidized or boiling state. Accordingly, the solid precipitation device is also sometimes referred to as a fluidized bed reactor or a boiling bed reactor.

[0077] According to one embodiment of the present application, the solid particles can be of any size and shape suitable for packing into the solid precipitation device. In particular, the equivalent diameter of the solid particles is generally 0.1-1.0 mm, and preferably 0.2-0.7 mm. In addition, the specific surface area of the solid particles is generally 100-300 m 2 / g, and the bulk density is generally 0.6-0.7 g / cm 3 .

[0078] According to one embodiment of the present application, as the packing amount of the solid particles in the solid precipitation device, for example, the amount (by volume) of the solid particles is generally 1 / 4-3 / 4, and preferably 1 / 4-1 / 2, of the total volume of the inner cavity of the housing.

[0079] According to one embodiment of the present application, as the plate, grid, net, cage, fiber and strip, etc., any structure and shape suitable for installation into the solid precipitation device is possible and is not particularly limited. For example, as the plate, a non-porous plate, in which case the precipitate is loaded on the plate surface, and a porous plate, in which case the precipitate is loaded on the plate surface and in the pores, can be mentioned.

[0080] According to the present application, when the solid particles are used as the carrier, continuous operation, i.e. continuous addition of the carrier to the solid precipitation device while continuously discharging the carrier loaded with the precipitate, is particularly suitable, as well as batch operation, i.e. periodic replacement of the carrier depending on the degree of loading with the precipitate; when the plate, grid, net, cage, fiber and strip, etc. are used as the carrier, batch operation, i.e. periodic replacement of the carrier depending on the degree of loading with the precipitate, is particularly suitable.

[0081] According to one embodiment of the present application, the carrier loaded with the precipitate discharged from the solid precipitation device can be regenerated by recovering the precipitate deposited on the carrier by means of ultrasound, high-temperature stirring, grinding, etc.

[0082] According to one embodiment of the present application, in the inner cavity of the housing, the residence time of the material is generally 10-1800 seconds, preferably 60-600 seconds or 10-180 seconds, and the space velocity is generally 1.5-270 h -1 .

[0083] According to one embodiment of the present application, the inner cavity of the housing of the solid precipitation device is operated under supercritical conditions, in particular under supercritical conditions of the solvent, such as water. Here, as the supercritical conditions, for example, an operating pressure of 23-35 MPaG, preferably 25-30 MPaG, and an operating temperature of 350-650°C, preferably 450-600°C or 450-550°C, can be mentioned.

[0084] According to one embodiment of the present application, in order to achieve the supercritical conditions, the carrier can be arranged in the inner cavity of the housing and its temperature can be higher than the supercritical temperature of the solvent, such as a temperature 1-15°C, 4-10°C or 6-8°C higher than the supercritical temperature. Here, the ratio of the carrier to the material is such that after mixing, the temperature of the material reaches or exceeds the supercritical temperature of the solvent.

[0085] According to one embodiment of the present application, in order to achieve the supercritical condition, the carrier can also be added to the inner cavity of the housing, and the temperature of the carrier is higher than the supercritical temperature of the solvent, such as 1-15°C, 4-10°C, or 6-8°C higher than the supercritical temperature. Here, the ratio of the carrier to the material is such that the temperature of the material reaches or exceeds the supercritical temperature of the solvent after mixing.

[0086] According to one embodiment of the present application, the solid precipitation device further comprises an inner member disposed in the inner cavity of the housing, particularly the upper portion. Here, the inner member comprises a hollow cylinder, particularly a hollow circular cylinder, which is substantially coaxial with the central axis of the housing. There must be a gap (referred to as the first gap) between the inner wall of the device housing and the outer wall of the hollow cylinder. In addition, the inner member further comprises a baffle located above the hollow cylinder. Preferably, the baffle is substantially coaxial with the central axis of the housing. In addition, there must be a gap (referred to as the second gap) between the baffle and the upper edge of the hollow cylinder, and a gap (referred to as the sixth gap) between the baffle and the inner wall of the housing, serving as an access channel for the relevant flow. As the aforementioned gaps, annular gaps are preferred.

[0087] According to one embodiment of the present application, the inner member is disposed in the upper portion of the inner cavity of the housing.

[0088] According to one embodiment of the present application, as the baffle, specific examples include a plate-like structure or a cap-like structure, particularly an umbrella canopy. Preferably, the umbrella canopy is coaxial with the hollow cylinder, and the taper angle is generally 30-150°, preferably 60-120°. In addition, although not particularly limited, the height of the baffle is generally 5-20% of the height of the inner cavity of the housing.

[0089] According to one embodiment of the present application, the hollow cylinder is open at both the upper and lower ends, comprising a straight cylinder segment at the upper portion and a conical diffusion segment at the lower portion. Here, the outer diameter of the straight cylinder segment of the hollow cylinder is generally 60-80%, preferably 67-73%, of the inner diameter of the housing. Although not particularly limited, the height of the straight cylinder segment of the hollow cylinder is generally 10-30% of the height of the inner cavity of the housing. Although not particularly limited, the maximum outer diameter of the conical diffusion segment of the hollow cylinder (i.e. the outer diameter of the bottom of the cone) is generally 75-90% of the inner diameter of the housing. Although not particularly limited, the height of the conical diffusion segment of the hollow cylinder is generally 3-10% of the height of the inner cavity of the housing.

[0090] According to one embodiment of the present application, the solid precipitation apparatus further comprises a guide structure arranged around the inner wall of the housing. The guide structure encloses the inner space of the housing to form a passage (referred to as a guide opening) which is open at the top and bottom, in particular a cylindrical passage which is open at the top and bottom. Preferably, the guide structure has a trapezoidal shape in a longitudinal section along the central axis of the housing, and the trapezoidal shape has an acute angle a and an acute angle β, preferably 5-70°. According to the present application, a gap (referred to as a third gap) must exist between the guide structure and the lower edge of the hollow cylinder. Preferably, the guide opening is substantially coaxial with the central axis of the housing. As the third gap, a ring-shaped gap is particularly preferred.

[0091] According to one embodiment of the present application, the inner diameter of the guide opening is generally 60-80% of the inner diameter of the housing. In addition, the height of the guide opening is generally 5-15% of the height of the inner space of the housing.

[0092] According to one embodiment of the present application, the guide structure is arranged below the hollow cylinder and above the material inlet, and is arranged in the upper part of the inner space of the housing.

[0093] According to one embodiment of the present application, the material inlet is located at the bottom or lower part of the housing. Here, the structure of the material inlet is suitable for injecting the material into the inner space of the housing. As the structure, for example, a nozzle or a liquid distributor, preferably a liquid distributor, in particular a liquid distribution disc, can be cited.

[0094] According to one embodiment of the present application, the material outlet is located at the top or upper part of the housing, in particular at the top of the housing. Preferably, the material outlet is located above the baffle.

[0095] According to one embodiment of the present application, the solid precipitation apparatus further comprises a carrier inlet and a carrier outlet. Here, the carrier inlet is generally located at the top or upper part of the housing, preferably at the top of the housing. Preferably, the carrier inlet is located above the guide structure, more preferably above the baffle. In addition, the carrier outlet is generally located at the bottom of the housing, preferably below the material inlet.

[0096] According to one embodiment of the present application, in order to achieve the supercritical condition, the solid precipitation apparatus can further comprise a hot agent inlet. Here, the hot agent inlet is located at the bottom or lower part of the housing, preferably at the bottom of the housing. In addition, the structure of the hot agent inlet is suitable for injecting the hot agent into the inner space of the housing. As the structure, for example, a nozzle or a gas distributor, preferably a gas distributor, in particular a gas distribution disc, can be cited. Preferably, the gas distributor is substantially coaxial with the central axis of the housing.

[0097] According to one embodiment of the present application, the heat agent is capable of raising the temperature of the material to reach or exceed the supercritical temperature of the solvent by physical heat exchange or chemical heat release or the like. As the heat agent, specifically, for example, an oxidizing gas such as air, oxygen or the like, or an oxidizing liquid (collectively referred to as an oxidizing agent) such as hydrogen peroxide, an aqueous peracid solution, or a heating gas such as steam (for example, steam of the solvent) can be cited. It is preferable that the amount of the heat agent be such that the material forms a supercritical state after entering the inner cavity of the housing, for example, reaches or exceeds the supercritical temperature of the solvent. For example, the ratio of the heat agent to the material is such that the temperature of the material is raised to reach or exceed the supercritical temperature of the solvent after mixing. Here, as the chemical heat release, for example, a case where the heat agent is chemically reacted with some or certain components contained in the material to release heat can be cited. In particular, in the case where the material is a salt-containing wastewater or a high-salt wastewater and the heat agent is the oxidizing gas, the oxidizing gas is oxidized with the organic contaminants in the salt-containing wastewater or the high-salt wastewater to release heat, thereby raising the temperature of the salt-containing wastewater or the high-salt wastewater to reach or exceed the supercritical temperature of water, or in the case where the salt-containing wastewater or the high-salt wastewater is maintained in a subcritical state before entering the solid precipitation device, raising the temperature by 4°C or more (preferably, 6 to 8°C) to reach or exceed the supercritical temperature of water.

[0098] According to one embodiment of the present application, the material is a salt-containing wastewater or a high-salt wastewater, particularly a high-salt organic wastewater, and the heat agent is the oxidizing gas, and the amount of the heat agent is 100 to 500%, preferably 150 to 350% of the oxidation theoretical oxygen demand of the material. Here, the oxidation theoretical oxygen demand is the amount of oxygen required for complete oxidation of COD in the organic wastewater.

[0099] According to one embodiment of the present application, the temperature, pressure, or the like of the heat agent when it is input into the inner cavity is not particularly limited. Here, as the temperature, for example, any temperature from normal temperature to the supercritical temperature of the solvent (particularly water) can be cited. As the pressure, for example, any pressure that can ensure input of the heat agent into the inner cavity can be cited, and more specifically, for example, a pressure substantially the same as that of the material can be cited.

[0100] According to one embodiment of the present application, particularly in the case where the material is a salt-containing wastewater or a high-salt wastewater (particularly a high-salt organic wastewater) with a COD greater than 20,000 mg / L (preferably 20,000-200,000 mg / L or 20,000-40,000 mg / L) and the thermal agent is the oxidizing gas, the temperature of the material can be raised to reach or exceed the supercritical temperature of the solvent (particularly water) even if the temperature of the thermal agent is far below the supercritical temperature of the solvent (particularly water), such as substantially normal temperature, thereby effectively achieving the technical effects intended by the present application.

[0101] According to one embodiment of the present application, in order to avoid large fluctuations in the temperature within the solid precipitation device, other organic wastewater, such as high-salt organic wastewater with a higher or lower COD, can be added to the material as appropriate to keep the COD content of the material substantially constant when entering the solid precipitation device.

[0102] According to one embodiment of the present application, the thermal agent inlet is located above or below the material inlet, preferably below the material inlet.

[0103] According to one embodiment of the present application, the solid precipitation device further comprises an inner cylinder (also a hollow cylinder structure). As the inner cylinder, for example, a straight cylinder or a trumpet cylinder, particularly a straight circular cylinder, can be mentioned. Preferably, the inner cylinder is substantially coaxial with the central axis of the shell.

[0104] According to one embodiment of the present application, the outer diameter of the inner cylinder is generally 60-80%, preferably 67-73%, of the inner diameter of the shell. In addition, the height of the inner cylinder is generally 20-60%, preferably 30-50%, of the height of the inner cavity of the shell.

[0105] According to one embodiment of the present application, the inner cylinder is located below the guide structure. In addition, the inner cylinder is preferably arranged in the lower part of the inner cavity of the shell.

[0106] According to one embodiment of the present application, there is a gap (referred to as a fourth gap), particularly an annular gap, between the inner wall of the shell and the outer wall of the inner cylinder. In addition, there is a gap (referred to as a fifth gap), particularly an annular gap, between the lower edge or inner wall of the inner cylinder and the thermal agent inlet. Here, the fifth gap communicates the fourth gap with the inner space of the inner cylinder. Preferably, the material inlet is arranged in the fourth gap and below the upper edge of the inner cylinder, further preferably the material inlet is 100-500 mm lower than the upper edge of the inner cylinder in the vertical direction.

[0107] According to one embodiment of the present application, the inner cylinder is configured such that substantially all of the thermal agent input from the thermal agent inlet enters the inner space of the inner cylinder. For example, referring to Figure 3 or Figure 4 , the thermal agent inlet is a gas distributor, and the inner cylinder is located above or contains the gas distributor, separated by the fifth gap. In the first case, the inner cylinder has a projection in the vertical direction on the gas distributor, and all gas outlets of the gas distributor are arranged in the projection area. The present application is not limited to this, and those skilled in the art can anticipate any possible configuration based on this requirement of the inner cylinder.

[0108] According to one embodiment of the present application, when the inner cavity space of the shell below the upper edge of the inner cylinder is referred to as a buffer zone, the buffer zone generally accounts for 25-40% or 20-60% of the total volume of the inner cavity of the shell.

[0109] According to one embodiment of the present application, in the buffer zone, the ratio of the thermal agent to the material is such that the temperature of the material increases to reach or exceed the supercritical temperature of the solvent when it leaves the upper edge of the inner cylinder, i.e. when it leaves the buffer zone. In particular, in the case where the material is salt-containing or high-salt wastewater and the thermal agent is the oxidizing gas, the organic pollutants in the wastewater release reaction heat during the oxidative decomposition process, resulting in the temperature of the wastewater being lower than the supercritical temperature of water when it is in the buffer zone, and the temperature of the wastewater increasing to reach or exceed the supercritical temperature of water when it leaves the buffer zone, thereby avoiding the precipitation of salt in the buffer zone.

[0110] According to one embodiment of the present application, as an operating method of the solid precipitation device, for example, the following can be mentioned: the material enters the lower part of the inner cavity of the shell from the material inlet, the carrier enters the upper part of the inner cavity of the shell from the carrier addition port, then passes through the first gap, the third gap and the guide port to enter the lower part of the inner cavity of the shell, the material makes the carrier flow, at least a part of the solute is deposited and loaded on the carrier to form a loaded carrier, a part of the loaded carrier moves to the bottom of the inner cavity of the shell, is discharged from the carrier discharge port, another part of the loaded carrier moves with the material from which at least a part of the solute has been removed (referred to as purified material) to the upper part of the inner cavity of the shell, passes through the guide port, enters the straight cylinder section from the conical diffusion section, and then is discharged from the second gap, the loaded carrier flows back to the lower part of the inner cavity of the shell via the first gap, the third gap and the guide port, and the purified material moves to the top of the inner cavity of the shell via the sixth gap and is discharged from the discharge port.

[0111] According to one embodiment of the present application, as another operation method of the solid precipitation device, for example, the carrier enters the upper portion of the inner cavity of the shell from the carrier inlet, then enters the lower portion of the inner cavity of the shell via the first gap, the third gap and the guide port, the material enters the fourth gap from the material inlet, then enters the inner space of the inner cylinder via the fifth gap, mixes with the heating agent entering the inner space of the inner cylinder from the heating agent inlet to form a mixture, the mixture is discharged from the upper edge of the inner cylinder after the temperature is increased to reach or exceed the supercritical temperature of the solvent, a part of the mixture flows back to the inner space of the inner cylinder via the fourth gap and the fifth gap (forming an internal circulation), another part of the mixture makes the carrier in a flow state, at least a part of the solute is deposited and loaded on the carrier to form a loaded carrier, a part of the loaded carrier moves to the bottom of the inner cavity of the shell via the fourth gap, is discharged from the carrier discharge port of the inner cavity of the shell, another part of the loaded carrier moves with the mixture from which at least a part of the solute is removed (referred to as a purified mixture) to the upper portion of the inner cavity of the shell, passes through the guide port, enters the straight cylinder section from the tapered diffusion section, and is then discharged from the second gap, the loaded carrier flows back to the lower portion of the inner cavity of the shell via the first gap, the third gap and the guide port, and the purified mixture moves to the top of the inner cavity of the shell via the sixth gap, and is discharged from the discharge port of the inner cavity of the shell.

[0112] According to one embodiment of the present application, according to the situation, a pH adjusting agent can be added to the material and / or to the inner cavity of the shell, and the amount of the pH adjusting agent is such that the pH value of the content in the inner cavity of the shell is maintained at 9-13. Here, as the pH adjusting agent, any agent that can be used in the art to adjust the pH value can be mentioned, and there is no particular limitation, and specifically, for example, sodium hydroxide and potassium hydroxide, etc. can be mentioned. For this purpose, the solid precipitation device can also be provided with a pH adjusting device to adjust the material to an alkaline environment, thereby preventing device corrosion.

[0113] According to one embodiment of the present application, according to the situation, the solid precipitation device can also be provided with a heat exchange device. The heat exchange device is used for heat recovery between the discharged material of the solid precipitation device (such as the purified material discharged from the material outlet) and the feed material of the solid precipitation device (such as the material fed from the material inlet).

[0114] According to one embodiment of the present application, it is obvious to those skilled in the art that any component of the solid precipitation device, such as the device shell and inner member, etc., can be resistant to the supercritical conditions (especially high temperature and high pressure) of the solvent in terms of material and structure. Therefore, especially when used for desalination of high-salinity wastewater, the design pressure of these components is generally not less than 35 MPa, and the design temperature is generally not less than 650℃.

[0115] According to one embodiment of the present application, it also relates to a solid precipitation method, especially a desalination method. The method comprises introducing the material of any one of the aspects described above into the solid precipitation device of any one of the aspects described above, and depositing and loading the precipitate on the carrier.

[0116] The present application will be described in detail below with reference to the drawings, taking the desalination of high-salinity wastewater as an example, but the present application is not limited thereto.

[0117] The drawings will be described below in conjunction with Figure 1 The desalination method of the present application will be described in more detail.

[0118] The wastewater first enters the heat exchanger 1, exchanges heat with the high-temperature liquid after gas-liquid separation, and then enters the ebullated bed reactor 2 for supercritical water oxidation treatment. After oxidation, the wastewater can be discharged after gas-liquid separation. The ebullated bed reactor used is a conventional reactor in the art, mainly including a reactor shell, a gas-liquid distribution plate, and conventional components such as solid particles. The solid particles in the ebullated bed reactor are periodically added and discharged from the ebullated bed reactor through an online addition and discharge system, including a solid particle online addition system 4 and a solid particle online discharge system 5. The solid particle online addition system 4 includes a feeding hopper, a feeding tank, and a valve. When it is necessary to add to the reactor, first close the valve between the feeding tank and the reactor, then open the vent valve to empty the feeding tank, and then use gas transmission or liquid transmission or rely on gravity to add the solid particles in the feeding hopper to the feeding tank, then close the valve on the pipeline, and then fill nitrogen into the feeding tank through a nitrogen pressurizing valve to make the pressure in the feeding tank substantially equal to the pressure in the reactor. Then open the valve of the pipeline connecting the feeding tank and the reactor, and the particles enter the reactor by gravity. The solid particle online discharge system 5 includes a solid particle discharge tank and a valve. Before discharging the salt-containing solid particles from the reactor, first close the valve on the pipeline connecting the bottom of the reactor and the salt-containing solid particle discharge tank, fill the tank with feed wastewater, then introduce high-pressure nitrogen to the reaction pressure, open the valve on the pipeline connecting the bottom of the reactor and the salt-containing solid particle discharge tank, and the particles enter the solid particle discharge tank from the bottom of the reactor due to gravity.

[0119] The drawings will be described below in conjunction with Figure 2 The structural features and working principles of the desalination device of the present application are as follows:

[0120] The desalination device comprises a device shell 5 and a desalination device inner member, wherein the desalination device inner member comprises a guide structure 7, a hollow cylinder 8 and an umbrella-shaped top 9. The hollow cylinder 8 and the umbrella-shaped top 9 located at the upper part of the hollow cylinder are arranged higher than the guide structure 7, the upper and lower ends of the hollow cylinder are all open, the lower end is a conical diffusion section, and the umbrella-shaped top 9 is concentric with the hollow cylinder 8. The lower end opening of the hollow cylinder 8 is a flow guide opening 6, and the annular opening formed by the lower end opening of the hollow cylinder and the inner wall of the desalination device is a backflow opening for solid particles in the desalination device, and the separated solid particles return to the lower part of the desalination device.

[0121] The high-salinity wastewater enters the desalination device through the raw material inlet 1 and is uniformly distributed in the desalination device after passing through the liquid distributor 3, so that the solid particles 4 are in a flowing state. Under the carrying action of the flow, the particle bed layer expands to a certain height, and desalination reaction is carried out in the desalination device, so that the salts are deposited on the particles. The reacted material will carry part of the particles into the hollow cylinder 8 and the umbrella-shaped top 9 through the guide opening 6 surrounded by the guide structure 7 for separation, the separated particles flow back to the lower part of the desalination device through the outer side of the cylindrical structure inner member, and the desalted wastewater is discharged from the desalination device through the discharge port 10. In order to timely discharge the saturated solid particles from the desalination device and supplement fresh particles, fresh particles can be supplemented to the reaction system through the solid particle adding port 11 at the upper part of the desalination device, and the solid particles are discharged from the reaction system through the solid particle discharge port 2 at the lower part of the desalination device.

[0122] In combination with the drawings Figure 3 , the structural features and working principles of the desalination device of the present application are as follows:

[0123] In combination with the drawings Figure 2 , an inner cylinder 12 and a gas distributor 3 are arranged in the lower part of the desalination device, the gas distributor replaces the position of the liquid distributor, the inner cylinder 12 is located above the gas distributor, and wastewater inlets 13 are arranged at the bottom ends of the two sides of the desalination device, and the wastewater symmetrically enters the annular system between the buffer zone inner cylinder and the inner wall of the device shell.

[0124] The high-salinity wastewater enters the annular system between the buffer zone inner cylinder and the inner wall of the device shell through the two symmetric wastewater inlets 13 in the lower part of the desalination device, and an internal circulation is formed in the buffer zone during operation. The gas enters the buffer zone through the gas inlet 1 and the gas distributor 3, and the solid particles are in a flowing state under the action of the gas and the liquid. The temperature of the buffer zone increases by 4-8℃ after the reaction, and then enters the upper part of the desalination device. The reaction is carried out under a certain temperature and pressure, so that the salts in the high-salinity wastewater are deposited on the solid particles. With the progress of the reaction, the solid particles with deposited salts move downward to the solid particle discharge port. After the gas-solid two-phase separation, the solid phase returns to the desalination device, and the gas phase is discharged from the desalination device.

[0125] In combination with the drawings Figure 4 , the structural features and working principles of the desalination device of the present application are as follows:

[0126] The desalination device includes a housing 6 and internal components, wherein the internal components include a hollow cylinder 7, an inner cylinder 4, and a cap 8. The hollow cylinder is open at both the top and bottom.

[0127] High-salinity wastewater enters the annular system between the inner cylinder 4 and the outer wall of the device through two or more symmetrical inlets at the bottom. The gas phase enters the device from the bottom of the inner cylinder 4, while solid particles enter from the top. Due to the difference in gas content inside and outside the inner cylinder, an internal circulation is formed. In the upper part of the inner cylinder, a portion of the gas-liquid-solid mixture flows upward into the hollow cylinder 7, while the other portion enters the annular system between the inner cylinder 4 and the outer wall of the device, passing through gaps 4 and 3 to enter the interior of the hollow cylinder. The gas-liquid-solid mixture inside the hollow cylinder 7 flows upward, reaching the top of the hollow cylinder 7 where gas-liquid-solid three-phase separation occurs. Solid particles and a portion of the liquid phase enter the annular system between the hollow cylinder 7 and the outer wall of the device through gaps 2 and 1, flowing back to the bottom of the device. The gas phase and a portion of the liquid phase exit the device through outlet 9 at the top, completing the gas-liquid separation process.

[0128] Example

[0129] The present invention will be further described in detail below through embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0130] In the following examples and comparative examples, all test methods used, unless otherwise specified, are conventional methods in the art, and all test materials used, unless otherwise specified, were purchased from conventional biochemical reagent stores.

[0131] Example 1

[0132] Using the appendix of this invention Figure 1 The process shown has a COD concentration of 92,600 mg / L, a TDS of 13.5 wt%, and a pH of 8.5 in the high-salt organic wastewater.

[0133] High-salt organic wastewater and oxygen are introduced into a fluidized bed reactor. The solid particles in the fluidized bed reactor are alumina ceramic spheres with a diameter of 0.4 mm and a bulk density of 0.65 g / cm³. 3 Specific surface area is 260m² 2 The solid particle addition rate is 1 / 2 of the reactor volume. The oxidant feed rate is 300% of the theoretical oxygen demand for wastewater oxidation. The supercritical oxidation conditions are: reaction temperature 600℃, reaction pressure 28MPa, and reaction residence time 30 seconds. The solid particle addition and discharge rate during the reaction process is 75 g·h⁻¹. -1 ·L -1 进水The salts in the wastewater are deposited on the solid particles in the boiling bed reactor, and after the reaction, the liquid phase can be discharged after heat exchange with the reactor feed wastewater, or the feed wastewater is diluted, so that the COD content entering the supercritical water oxidation reactor is kept stable, the reaction is carried out smoothly, and the temperature in the reactor is prevented from fluctuating greatly.

[0134] After the above treatment, the concentration of COD in the effluent is 46 mg / L, and the TDS is 25 mg / L, which meets the direct discharge requirement.

[0135] Example 2

[0136] The process shown in the accompanying drawings of the present application is adopted. Figure 1 In the high-salt organic wastewater, the COD concentration is 21700 mg / L, the TDS is 5.3 wt%, and the pH is 8.

[0137] The high-salt organic wastewater and oxygen are introduced into the boiling bed reactor, wherein the solid particles in the boiling bed reactor are alumina ceramic pellets with a diameter of 0.2 mm and a bulk density of 0.67 g / cm 3 The specific surface area of the solid particles is 100 m 2 / g, and the amount of the solid particles added is 1 / 3 of the volume of the reactor. The amount of the oxidant introduced is 150% of the theoretical oxygen demand of the wastewater oxidation. The supercritical oxidation conditions are as follows: the reaction temperature is 380 DEG C, the reaction pressure is 23 MPa, and the reaction residence time is 150 seconds. The amount of the solid particles added and discharged during the reaction is 58 g·h -1 ·L -1 进水 The salts in the wastewater are deposited on the solid particles in the boiling bed reactor, and after the reaction, the liquid phase can be discharged after heat exchange with the reactor feed wastewater, or the feed wastewater is diluted, so that the COD content entering the supercritical water oxidation reactor is kept stable, the reaction is carried out smoothly, and the temperature in the reactor is prevented from fluctuating greatly.

[0138] After the above treatment, the concentration of COD in the effluent is 58 mg / L, and the TDS is 113 mg / L, which meets the direct discharge requirement.

[0139] Example 3

[0140] The process shown in the accompanying drawings of the present application is adopted. Figure 1 In the high-salt organic wastewater, the COD concentration is 137200 mg / L, the TDS is 14.3 wt%, and the pH is 8.7.

[0141] The high-salt organic wastewater and oxygen are introduced into the boiling bed reactor, wherein the solid particles in the boiling bed reactor are alumina ceramic pellets with a diameter of 0.7 mm and a bulk density of 0.62 g / cm 3The specific surface area is 300 m 2 / g, and the solid particle addition amount is 1 / 2 of the reactor volume. The amount of the oxidant introduced is 350% of the theoretical oxygen demand of the wastewater oxidation. The supercritical oxidation conditions are: the reaction temperature is 650 DEG C, the reaction pressure is 30 MPa, and the reaction residence time is 30 seconds. The solid particle addition and discharge amount during the reaction is 79 g·h -1 ·L -1 进水 The salt in the wastewater is deposited on the solid particles in the boiling bed reactor, and the organic matter in the wastewater is oxidized and decomposed into carbon dioxide and water. After the reaction, the liquid phase can be discharged after heat exchange with the reactor feed wastewater, or the feed wastewater is diluted to keep the COD content in the supercritical water oxidation reactor stable, so that the reaction can proceed smoothly, and the temperature in the reactor can be prevented from fluctuating greatly.

[0142] After the above treatment, the concentration of COD in the effluent is 54 mg / L, and the TDS is 23 mg / L, which meets the direct discharge requirements.

[0143] Example 4

[0144] The same as example 1, except that the oxidant is air. After the above treatment, the concentration of COD in the effluent is 59 mg / L, and the TDS is 26 mg / L.

[0145] Example 5

[0146] The same as example 1, except that the solid particles are silica beads with a diameter of 0.5 mm and a specific surface area of 230 m 2 / g. After the above treatment, the concentration of COD in the effluent is 53 mg / L, and the TDS is 62 mg / L.

[0147] Example 6

[0148] The same as example 1, except that sodium hydroxide is added to the feed wastewater to control the influent pH to be 11. After the above treatment, the COD and TDS in the effluent change little. However, by controlling the influent pH to be alkaline, the alkaline substances in the wastewater can neutralize the acidic substances generated during the reaction, thereby avoiding corrosion of the reactor.

[0149] Example 7

[0150] The solid particles used in the present application are not limited to the above-mentioned solid particles, and other solid particles with similar properties can also be used. Figure 2The desalination device shown has an inner cavity height of 2m and an inner diameter of 0.17m. The outer diameter of the hollow straight section is 0.12m, and the height of the hollow straight section is 0.4m. The umbrella-shaped cone angle is 100°, the umbrella-shaped cone height is 0.25m, and the outer diameter of the umbrella-shaped cone is 0.14m. The maximum outer diameter of the conical diffuser section is 0.14m, and the height of the conical diffuser section is 0.15m. The guiding structure is a trapezoidal cross-section ring structure with a height of 0.2m and an inner diameter of the guide opening of 0.13m. The coverage angle α is 45°, and the friction angle β is 45°. The TDS in the high-salt organic wastewater is 13.5wt%, and the pH is 8.5.

[0151] High-salt organic wastewater (temperature 360℃, pressure 30MPa) is passed into a desalination device, where the solid particles are alumina ceramic spheres with a diameter of 0.4mm and a bulk density of 0.65g / cm³. 3 Specific surface area is 260m² 2 The solid particle addition rate is 1 / 2 of the device volume. The operating temperature of the device cavity is 600℃, the pressure is 28MPa, and the residence time is 30 seconds. The solid particle addition and discharge rate is 75 g·h. -1 ·L -1 Influent. After treatment, the TDS in the effluent was 113 mg / L.

[0152] After 100 days of continuous operation, no blockages occurred in the equipment or pipelines.

[0153] Example 8

[0154] Using the appendix of this invention Figure 3 The desalination device shown has an inner cavity with a height of 2m and an inner diameter of 0.17m. The outer diameter of the hollow straight section is 0.12m, and the height of the hollow straight section is 0.4m. The umbrella-shaped cone angle is 100°, the umbrella-shaped cone height is 0.25m, and the outer diameter of the umbrella-shaped cone is 0.14m. The maximum outer diameter of the conical diffuser section is 0.14m, and the height of the conical diffuser section is 0.15m. The guiding structure is a trapezoidal cross-section ring structure with a height of 0.2m. The guide opening has an inner diameter of 0.13m, a coverage angle α of 45°, a friction angle β of 45°, and an outer diameter of 0.12m and a height of 0.7m for the inner cylinder. The inlet for high-salt organic wastewater is 200mm lower vertically than the top edge of the inner cylinder. The high-salt organic wastewater has a COD concentration of 92600mg / L, a TDS of 13.5wt%, and a pH of 8.5.

[0155] High-salt organic wastewater (at ambient temperature and 30 MPa pressure) and oxygen (at ambient temperature and 30 MPa pressure) are introduced into a desalination device. The solid particles in the desalination device are alumina ceramic spheres with a diameter of 0.4 mm and a bulk density of 0.65 g / cm³. 3 Specific surface area is 260m² 2The solid particle addition rate is 1 / 2 of the device volume. The oxygen injection rate is 300% of the theoretical oxygen demand for wastewater oxidation. The operating temperature inside the device is 600℃, the pressure is 28MPa, and the residence time is 30 seconds. The solid particle addition and discharge rate is 75 g·h. -1 ·L -1 Influent. After treatment, the COD concentration in the effluent is 54 mg / L and the TDS is 63 mg / L, meeting the requirements for direct discharge.

[0156] After 100 days of continuous operation, no blockages occurred in the equipment or pipelines.

[0157] Example 9

[0158] Using the appendix of this invention Figure 4 The desalination device shown has an inner cavity height of 2m and an inner diameter of 0.17m. The outer diameter of the hollow straight section is 0.12m, and the height of the hollow straight section is 0.4m. The umbrella-shaped cone angle is 100°, the umbrella-shaped cone height is 0.25m, and the outer diameter of the umbrella-shaped cone is 0.12m. The outer diameter of the inner cylinder is 0.12m, and the height is 0.7m. The inlet for high-salt organic wastewater is 150mm lower vertically than the top edge of the inner cylinder. The high-salt organic wastewater has a COD concentration of 92600mg / L, a TDS of 13.5wt%, and a pH of 8.5.

[0159] High-salt organic wastewater (at ambient temperature and 30 MPa pressure) and oxygen (at ambient temperature and 30 MPa pressure) are introduced into a desalination device. The solid particles in the desalination device are alumina ceramic spheres with a diameter of 0.4 mm and a bulk density of 0.65 g / cm³. 3 Specific surface area is 260m² 2 The solid particle addition rate is 1 / 2 of the device volume. The oxygen injection rate is 300% of the theoretical oxygen demand for wastewater oxidation. The operating temperature inside the device is 600℃, the pressure is 28MPa, and the residence time is 30 seconds. The solid particle addition and discharge rate is 75 g·h. -1 ·L -1 Influent. After the above treatment, the COD concentration in the effluent is 46 mg / L and the TDS is 43 mg / L, which meets the requirements for direct discharge.

[0160] After 100 days of continuous operation, no blockages occurred in the equipment or pipelines.

[0161] Example 10

[0162] Same as Example 8, except that: the solid particles are silica microspheres with a diameter of 0.5 mm and a specific surface area of ​​230 μm. 2 / g. After the above treatment, the COD concentration in the effluent was 53 mg / L, and the TDS was 62 mg / L.

[0163] Example 11

[0164] The same as Example 8, except that sodium hydroxide was added to the high-salt organic wastewater feed to control the influent pH to 11. After the above treatment, the effluent COD and TDS changed little. However, by controlling the influent pH to be alkaline, the alkaline substances in the wastewater can neutralize the acidic substances generated during the desalination process, thereby avoiding corrosion of the device.

[0165] Example 12

[0166] The same as Example 7, except that the hollow cylinder, umbrella, and guide structure were not provided. After the above treatment, the effluent TDS was 436 mg / L.

[0167] After 30 days of continuous operation, the device and the pipeline were slightly clogged.

[0168] Comparative Example 1

[0169] The same as Example 1, except that a common reactor was used instead of a boiling bed reactor. After the above treatment, the effluent COD concentration was 96 mg / L, and the TDS was 138700 mg / L. The reactor and the pipeline were both clogged.

[0170] Comparative Example 2

[0171] The same as Example 1, except that a boiling bed reactor was used, and the treatment was carried out at a reaction temperature of 270°C, a reaction pressure of 9.0 MPa, and a residence time of 1 h. After the above treatment, the effluent COD concentration was 13790 mg / L, and the TDS was 14270 mg / L.

[0172] Comparative Example 3

[0173] The same as Example 7, except that no solid particles were added to the device. After the above treatment, the effluent TDS was 138700 mg / L.

[0174] After only 1 day of continuous operation, the device and the pipeline were severely clogged.

Claims

1. A solid precipitation method, comprising: feeding a material comprising a solute and a solvent into a solid precipitation device, wherein the solid precipitation device comprises a housing, a material inlet, a material outlet, a hot agent inlet, and a carrier disposed in an inner cavity of the housing, and wherein the carrier is a solid particle selected from at least one of a seed crystal, an alumina ball, a silica ball, sand, quartz sand, ceramsite, and a solid waste, and wherein a structure of the material inlet is adapted to spray the material into the inner cavity of the housing, and wherein the solid precipitation device further comprises a carrier addition inlet and a carrier discharge outlet, wherein the carrier addition inlet is located at a top or an upper portion of the housing, and wherein the carrier discharge outlet is located below the material inlet, and wherein the solid precipitation device further comprises an inner member disposed in the inner cavity of the housing, wherein the inner member comprises a hollow cylinder coaxial with a central axis of the housing, and wherein the hollow cylinder comprises a straight cylinder section at an upper portion and a tapered diffusion section at a lower portion, and wherein a gap exists between an inner wall of the device housing and an outer wall of the hollow cylinder, and wherein the gap is referred to as a first gap, and wherein the inner member further comprises a baffle located above the hollow cylinder, and wherein the baffle is coaxial with the central axis of the housing, and wherein a gap exists between the baffle and an upper edge of the hollow cylinder, and wherein the gap is referred to as a second gap, and wherein a gap exists between the baffle and the inner wall of the housing, and wherein the gap is referred to as a sixth gap, and wherein the material outlet is located above the baffle, and wherein the carrier addition inlet is located above the baffle, and wherein the baffle is an umbrella, and wherein the material outlet is a material outlet, and wherein the solid precipitation device further comprises a guide structure disposed around the inner wall of the housing, and wherein the guide structure encircles the inner cavity of the housing to form an upwardly and downwardly open channel, and wherein the channel is referred to as a guide outlet, and wherein the guide structure is disposed below the hollow cylinder and above the material inlet, and wherein a gap exists between the guide structure and a lower edge of the hollow cylinder, and wherein the gap is referred to as a third gap, and wherein the solid precipitation device further comprises an inner cylinder, and wherein the hot agent inlet is located at a bottom of the housing, and wherein a gap exists between the inner wall of the housing and an outer wall of the inner cylinder, and wherein the gap is referred to as a fourth gap, and wherein a gap exists between a lower edge or an inner wall of the inner cylinder and the hot agent inlet, and wherein the gap is referred to as a fifth gap, and wherein the fifth gap is in communication with the fourth gap and an inner space of the inner cylinder, and wherein a configuration of the inner cylinder is such that the hot agent input from the hot agent inlet enters the inner space of the inner cylinder entirely, and wherein the material inlet is disposed in the fourth gap and below an upper edge of the inner cylinder, and wherein a space of the inner cavity of the housing below the upper edge of the inner cylinder is referred to as a buffer zone, and wherein a ratio of the hot agent to the material in the buffer zone is such that a temperature of the material increases to reach or exceed a supercritical temperature of the solvent when the material exits the upper edge of the inner cylinder, thereby avoiding precipitation of a salt in the buffer zone. The device is a desalination device, and / or the housing is a vertical cylindrical housing, and / or the material is a salt-containing wastewater or a high-salt wastewater comprising a solvent and a solute. ​ ​ ​ ​ 2. The solid precipitation method according to claim 1, wherein, ​ 3. The solid precipitation method according to claim 1, operating under supercritical conditions.

4. The solid precipitation method according to claim 3, wherein, The device is operating under supercritical conditions of water.

5. The solid precipitation method according to claim 1, wherein the inner member is arranged in the upper part of the inner cavity of the shell, and / or the first gap is an annular gap, and / or the second gap is an annular gap, and / or the sixth gap is an annular gap.

6. The solid precipitation method according to claim 1, wherein the umbrella is coaxial with the hollow cylinder, the cone angle is 30-150°, and / or the outer diameter of the straight section of the hollow cylinder is 60-80% of the inner diameter of the shell, and / or the height of the straight section of the hollow cylinder is 10-30% of the height of the inner cavity of the shell, and / or the maximum outer diameter of the conical diffusion section of the hollow cylinder is 75-90% of the inner diameter of the shell, and / or the height of the conical diffusion section of the hollow cylinder is 3-10% of the height of the inner cavity of the shell, and / or the height of the baffle is 5-20% of the height of the inner cavity of the shell.

7. The solid precipitation method according to claim 6, wherein the cone angle is 60-120°, and / or the outer diameter of the straight section of the hollow cylinder is 67-73% of the inner diameter of the shell.

8. The solid precipitation method according to claim 1, wherein the guide port is coaxial with the central axis of the shell, and / or the guide structure is arranged in the upper part of the inner cavity of the shell.

9. The solid precipitation method according to claim 1, wherein the guide structure is trapezoidal in longitudinal section along the central axis of the shell, and / or the acute angles α and β of the trapezoid are 5-70°, and / or the guide port is a cylindrical passage, and / or the third gap is an annular gap.

10. The solid precipitation method according to claim 1, wherein the ratio of the height of the inner cavity of the shell, in meters, to the inner diameter, in meters, is 7-17, and / or the inner diameter of the guide port is 60-80% of the inner diameter of the shell, and / or the height of the guide port is 5-15% of the height of the inner cavity of the shell.

11. The solid precipitation method according to claim 10, wherein the structure of the material inlet is a nozzle or a liquid distributor, and / or the ratio of the height of the inner cavity of the shell, in meters, to the inner diameter, in meters, is 10-14.

12. The solid precipitation method according to claim 1, wherein the thermal agent is air, oxygen or other heating gas, and / or the structure of the thermal agent inlet is a nozzle or a gas distributor, and / or the thermal agent inlet is located below the material inlet.

13. The solid precipitation method according to claim 1, wherein the buffer zone occupies 20-60% of the total volume of the inner cavity of the shell, and / or the structure of the thermal agent inlet is a gas distributor, and the inner cylinder is located above or contains the gas distributor, separated by the fifth gap, and / or the inner cylinder is located below the guiding structure, and / or the material inlet is 100-500 mm lower than the upper edge of the inner cylinder in the vertical direction, and / or the outer diameter of the inner cylinder is 60-80% of the inner diameter of the shell, and / or the height of the inner cylinder is 20-60% of the height of the inner cavity of the shell, and / or the inner cylinder is arranged in the lower part of the inner cavity of the shell.

14. The solid precipitation method according to claim 13, wherein the inner cylinder is straight cylindrical or trumpet-shaped, and / or the inner cylinder is coaxial with the central axis of the shell, and / or the buffer zone occupies 25-40% of the total volume of the inner cavity of the shell, and / or the gap between the inner wall of the shell and the outer wall of the inner cylinder is an annular gap, and / or the gap between the lower edge or inner wall of the inner cylinder and the thermal agent inlet is an annular gap, and / or the thermal agent inlet is substantially coaxial with the central axis of the shell, and / or the outer diameter of the inner cylinder is 67-73% of the inner diameter of the shell, and / or the height of the inner cylinder is 30-50% of the height of the inner cavity of the shell.

15. The solid precipitation method according to claim 1, wherein the material is kept in a subcritical state before entering the solid precipitation device, and / or the temperature of the carrier is higher than the supercritical temperature of the solvent, and / or the carrier is added to the inner cavity of the shell, and the temperature of the carrier is higher than the supercritical temperature of the solvent, and / or the ratio of the carrier to the material is such that after mixing, the temperature of the material reaches or exceeds the supercritical temperature of the solvent.

16. The solid precipitation method according to claim 15, wherein the material is at room temperature or a temperature 1-15°C lower than the supercritical temperature of the solvent before entering the solid precipitation device, and / or the material is at or above the supercritical pressure of the solvent but at a temperature lower than the supercritical temperature of the solvent before entering the solid precipitation device, and / or the temperature of the carrier is 1-15°C higher than the supercritical temperature of the solvent, and / or the temperature of the carrier added to the inner cavity of the shell is 1-15°C higher than the supercritical temperature of the solvent.

17. The solid precipitation method according to claim 16, wherein the material is at room temperature or a temperature 6-8°C lower than the supercritical temperature of the solvent before entering the solid precipitation device, and / or the temperature of the carrier is 6-8°C higher than the supercritical temperature of the solvent, and / or the temperature of the carrier added to the inner cavity of the shell is 6-8°C higher than the supercritical temperature of the solvent.

18. The solid precipitation method according to claim 1, wherein the residence time of the material is 60-600 seconds.

19. The solid precipitation method according to claim 1, wherein a heat agent is added into the shell inner cavity, and the heat agent is used in an amount such that the material forms a supercritical state after entering the shell inner cavity, and / or the material is salt-containing wastewater or high-salt wastewater, the heat agent is an oxidizing gas, and / or the ratio of the heat agent to the material is such that after mixing, the temperature of the material reaches or exceeds the supercritical temperature of the solvent, and / or the ratio of the heat agent to the material is such that the temperature of the material reaches or exceeds the supercritical temperature of the solvent when leaving the upper edge of the inner cylinder, and / or the heat agent is used in an amount of 100-500% of the theoretical oxygen demand of the material for oxidation.

20. The solid precipitation method according to claim 19, wherein the material is high-salt organic wastewater, and / or the heat agent is oxygen or air, and / or the heat agent is used in an amount of 150-350% of the theoretical oxygen demand of the material for oxidation.

21. The solid precipitation method according to claim 1, wherein a pH regulator is added to the material and / or to the shell inner cavity, and the pH regulator is used in an amount such that the pH value of the contents in the shell inner cavity is maintained at 9-13.

22. The solid precipitation method according to claim 1, wherein the carrier enters the upper part of the shell inner cavity from the carrier inlet port, then enters the lower part of the shell inner cavity via the first gap, the third gap and the guide port, the material enters the fourth gap from the material inlet port, then enters the inner space of the inner cylinder via the fifth gap, mixes with the heat agent entering the inner space of the inner cylinder from the heat agent inlet port to form a mixture, and the mixture is discharged from the upper edge of the inner cylinder after the temperature is raised to reach or exceed the supercritical temperature of the solvent, a part of the mixture backflows to the inner space of the inner cylinder via the fourth gap and the fifth gap to form an internal circulation, another part of the mixture makes the carrier in a flowing state, at least a part of the solute is deposited and loaded on the carrier to form a loaded carrier, a part of the loaded carrier moves to the bottom of the shell inner cavity via the fourth gap, is discharged from the carrier discharge port to the shell inner cavity, another part of the loaded carrier moves to the upper part of the shell inner cavity with the mixture from which at least a part of the solute is removed, referred to as a purified mixture, passes through the guide port, enters the straight cylinder section from the conical diffusion section, and is then discharged from the second gap, and this part of the loaded carrier backflows to the lower part of the shell inner cavity via the first gap, the third gap and the guide port, and the purified mixture moves to the top of the shell inner cavity via the sixth gap, and is discharged from the shell inner cavity from the discharge port.

23. The solid precipitation method according to claim 1, wherein the material is high-salt wastewater, the TDS of the high-salt wastewater is not higher than 20 wt%, and the COD is greater than 20000 mg / L.

24. The solid precipitation method according to claim 23, wherein the material is high-salinity organic wastewater, and / or, the TDS of the high-salinity wastewater is 5-20 wt%, and / or, the COD is 20000-40000 mg / L.

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