Apparatus and applications and supercritical water oxidation reaction process for organic waste liquid

Abstract

The present application relates to the technical field of efficient degradation treatment of organic waste liquid, and discloses a device and application and a method for treating organic waste liquid by supercritical water oxidation reaction, which comprises a first shell, a reaction cavity defined by the first shell, a gas-phase product outlet and a solid-liquid product outlet connected to the reaction cavity; the reaction cavity comprises a material distribution section, a plurality of first nozzle rings and a plurality of second nozzle rings are arranged on the cavity wall of the material distribution section in an axial direction, and the first nozzle rings and the second nozzle rings are arranged alternately; each first nozzle ring comprises a plurality of first nozzles arranged in a ring shape in a circumferential direction, and the first nozzles are used for feeding first raw materials; each second nozzle ring comprises a plurality of second nozzles arranged in a ring shape in a circumferential direction, and the second nozzles are used for feeding second raw materials. The present application can realize efficient removal of organic matters in high-concentration and hard-degradation organic waste liquid, and can realize the purpose of synchronous desalination and re-concentration, and can reduce salt deposition on the cavity wall of the reaction cavity and avoid corrosion.

Description

Technical Field

[0001] This invention relates to the field of efficient degradation treatment technology for organic waste liquid, specifically to equipment and applications, and a method for treating organic waste liquid by supercritical water oxidation reaction. Background Technology

[0002] Supercritical water oxidation (SCWO) technology has broad prospects in the treatment of organic wastewater, sludge, and solid waste, characterized by thorough treatment, rapid reaction, and no secondary pollution. Since the initial proposal of SCWO technology, which can completely destroy the structure of organic pollutants, domestic and foreign companies have conducted extensive research and scaled up its industrial applications. However, due to the corrosive substances contained in the waste liquid itself, such as halogens, sulfur, and phosphorus, the inorganic salts produced during supercritical water oxidation form thick deposits on the inner walls of the reaction equipment, which have a strong corrosive effect on the equipment, affecting the effective operation and safety of the device. Summary of the Invention

[0003] The purpose of this invention is to overcome the problems of salt deposition on the walls and treatment efficiency in the process of supercritical water oxidation for treating organic wastewater in the prior art. It provides equipment and applications, as well as a method for supercritical water oxidation to treat organic waste liquid, which can achieve efficient removal of organic matter from high-concentration, recalcitrant organic waste liquid and simultaneous desalination and reconcentration, while reducing salt deposition on the reaction chamber walls.

[0004] To achieve the above objectives, the present invention provides an apparatus comprising a first housing, a reaction chamber defined by the first housing, and a gaseous product outlet and a solid-liquid product outlet communicating with the reaction chamber.

[0005] The reaction chamber includes a material distribution section, and the chamber wall of the material distribution section is provided with a plurality of first nozzle rings and a plurality of second nozzle rings that are sequentially spaced along the axial direction, and the first nozzle rings and second nozzle rings are arranged alternately.

[0006] Each of the first nozzle rings includes a plurality of first nozzles arranged in a ring at circumferential intervals, the first nozzles being used to feed a first raw material;

[0007] Each of the second nozzle rings includes a plurality of second nozzles arranged in a ring at circumferential intervals, the second nozzles being used to feed a second raw material.

[0008] Preferably, the material distribution section is located in the region of the reaction chamber from top to bottom, which is the 1 / 3 to 2 / 3 of the total length.

[0009] Preferably, the first and second nozzles located at the upper part of the material distribution section have their spray directions tilted downwards, while the first and second nozzles located at the lower part of the material distribution section have their spray directions tilted upwards.

[0010] More preferably, the first and second nozzles located at the upper part of the material distribution section are inclined downward at 0 to 45°.

[0011] More preferably, the first and second nozzles located at the lower part of the material distribution section are inclined upward at 0 to 45°.

[0012] More preferably, the first nozzle and the second nozzle located in the middle of the material distribution section are horizontally arranged.

[0013] Preferably, the first housing is covered by a second housing, and the annular gap between the first housing and the second housing is provided with a first pipe connecting each of the first nozzles and a second pipe connecting each of the second nozzles.

[0014] Preferably, the first nozzle and / or the second nozzle of the material distribution section are distributed with sparser nozzles at the top and denser nozzles at the bottom.

[0015] Preferably, the outlet diameter of the first nozzle and / or the second nozzle in the material distribution section gradually increases from top to bottom.

[0016] Preferably, the first pipe and the second pipe are formed as a double spiral coil structure spirally wrapped around the first housing along the axial direction. One end of the first pipe is closed and the other end extends out of the second housing to form a first feed inlet. One end of the second pipe is closed and the other end extends out of the second housing to form a second feed inlet.

[0017] Preferably, a fixing member for fixing the double helical coil structure is provided in the annular gap; more preferably, the fixing member is a bracket located at the bottom end of the annular gap.

[0018] The application of the device of the present invention in a reaction is preferred in an oxidation reaction, and more preferably in a supercritical water oxidation reaction.

[0019] This invention provides a method for treating organic waste liquid using supercritical water oxidation, which is carried out in the equipment described in this invention and includes the following:

[0020] Under supercritical water oxidation reaction conditions, organic waste liquid is injected into the reaction chamber from the first nozzle, and a mixture containing a second oxidant is injected into the reaction chamber from the second nozzle. The organic waste liquid and the mixture come into contact and undergo supercritical water oxidation reaction to obtain gaseous products and solid products containing inorganic salts.

[0021] In this process, the gaseous product rises and is discharged from the gaseous product outlet, while the solid product containing inorganic salts redissolves in the subcritical region to form a solid-liquid product, which is then discharged from the solid-liquid product outlet.

[0022] Preferably, the organic waste liquid enters the first pipeline through the first inlet and is sprayed into the reaction chamber through each of the first nozzles.

[0023] Preferably, the mixture containing the second oxidant enters the second pipe through the second inlet and is sprayed into the reaction chamber through each of the second nozzles.

[0024] Preferably, the supercritical water oxidation reaction conditions include: a temperature of 380–600°C, more preferably 400–550°C; and a pressure of 22–30 MPa, more preferably 22–25 MPa.

[0025] The method includes:

[0026] 1) Provide supercritical water oxidation reaction conditions through the combustion of pre-combustion material: preheated pre-combustion material is introduced into each first nozzle, and preheated first oxidant is introduced into each second nozzle. The first oxidant and pre-combustion material combust and release heat in the reaction chamber to form a supercritical reaction zone that can provide supercritical water oxidation reaction conditions for step 2).

[0027] The supercritical reaction zone is surrounded by a subcritical zone with a lower temperature, which is used to dissolve the inorganic salts produced by the supercritical oxidation reaction.

[0028] 2) Supercritical water oxidation reaction: The pre-combustion material introduced into the first nozzle is switched to organic waste liquid, and the first oxidant introduced into the second nozzle is switched to a mixture containing a second oxidant. The organic waste liquid and the mixture come into contact in the supercritical reaction zone to undergo supercritical water oxidation reaction to obtain gaseous products and solid products containing inorganic salts.

[0029] In this process, the gaseous product rises and is discharged from the gaseous product outlet, while the solid product containing inorganic salts redissolves in the subcritical region to form a solid-liquid product, which is then discharged from the solid-liquid product outlet.

[0030] Preferably, the pre-combustion material and the organic waste liquid enter the first pipeline through the first inlet and are sprayed into the reaction chamber through each of the first nozzles.

[0031] Preferably, the first oxidant and the mixture containing the second oxidant enter the second pipe through the second inlet and are sprayed into the reaction chamber through each of the second nozzles.

[0032] Preferably, the preheating temperature of the pre-combustion material is 350–370°C.

[0033] Preferably, the preheating temperature of the first oxidant is 20–370°C.

[0034] Preferably, the supercritical water oxidation reaction is carried out in the presence of a catalyst, which is selected from homogeneous catalysts and / or heterogeneous catalysts;

[0035] More preferably, the homogeneous catalyst is selected from one or more of sodium hydroxide, soluble transition metal salts, basic salts, and heteropolyacids;

[0036] More preferably, the soluble transition metal salt includes a nitrate or a sulfate, and the soluble transition metal salt contains at least one of Cu, Fe, Mn, Ni and Co;

[0037] More preferably, the alkaline salt includes sodium carbonate and / or sodium bicarbonate;

[0038] More preferably, the heteropolyacid includes at least one of phosphotungstic acid, silicotungstic acid, or phosphomolybdic acid.

[0039] Preferably, the active component of the heterogeneous catalyst is selected from one or more of noble metal elements, activated carbon, and metal oxides;

[0040] More preferably, the noble metal element includes at least one of Pt, Pd, Rh, Ru, and Ag;

[0041] More preferably, the metal oxide includes one or more of MgO, NiO, MnO2 and Cr2O3.

[0042] Preferably, the pre-combustion material is selected from at least one of methanol aqueous solution, ethanol aqueous solution or isopropanol aqueous solution.

[0043] Preferably, the organic waste liquid comes from coal chemical or petrochemical sources.

[0044] Preferably, the organic waste liquid is selected from one or more of high-concentration organic wastewater, high-salt organic wastewater, and mixed-salt organic mother liquor.

[0045] Preferably, the first oxidant is selected from hydrogen peroxide or oxygen.

[0046] Preferably, the second oxidant is selected from one or more of air, oxygen, and hydrogen peroxide.

[0047] Preferably, the mixture further includes a combustion improver and a modifier.

[0048] Preferably, the combustion aid includes a combustion-supporting organic solvent; more preferably, the combustion-supporting organic solvent is selected from at least one of ethanol, isopropanol, or methanol.

[0049] Preferably, the regulator is selected from water, an alkaline solution, or an acidic solution.

[0050] The advantages of this invention compared to the prior art are as follows:

[0051] (1) In view of the problem of uneven premixing of reactants in traditional reactors, or the problem of needing to add an extra mixer to increase design difficulty and construction cost, the present invention can achieve full mixing of reactants and improve the treatment effect through the convection atomization spray design of multiple first nozzles and second nozzles; at the same time, it can reduce the deposition of solids on the inner wall surface.

[0052] (2) The equipment of the present invention has a scientific and reasonable overall design, simple structure, and convenient operation. By setting the first pipe and the second pipe in the annular gap, on the one hand, the exothermic reaction of supercritical water oxidation is used to exchange heat with the raw material to preheat the raw material, reduce energy consumption, and optimize the processing efficiency. On the other hand, after the heat exchange, the wall temperature of the reaction chamber is lower than the temperature of the supercritical reaction zone, which allows the salt adsorbed on the inner wall to dissolve into a liquid phase and flow down the wall to the bottom of the reactor for discharge.

[0053] (3) The present invention can stabilize the temperature and pressure during the reaction process and reduce the operational risk by controlling the feed rate and spray intensity of the reactants in real time.

[0054] Other advantages of the present invention will be described in detail in the specific embodiments, and will not be elaborated here. Attached Figure Description

[0055] Figure 1 This is a schematic diagram of the device according to a specific embodiment of the present invention.

[0056] Explanation of reference numerals in the attached figures

[0057] 1 First feed inlet; 2 Second feed inlet; 3 Gas phase product outlet; 4 Solid-liquid product outlet; 5 Top cover; 6 Second shell; 7 First shell; 8 Annular gap; 9 First pipe; 10 Second pipe; 11a First nozzle; 11b Second nozzle; 12 Supercritical reaction zone; 13 Support. Detailed Implementation

[0058] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0059] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0060] In this invention, unless otherwise stated, directional terms such as "upper," "lower," "left," and "right" generally refer to the upper, lower, left, and right positions shown in the accompanying drawings; "inner" and "outer" refer to the inner and outer positions relative to the outline of each component itself. In this invention, unless otherwise stated, the "upper part" of the container refers to the position of 0-30% of the container from top to bottom; the "middle part" of the container refers to the position of 30-70% of the container from top to bottom.

[0061] like Figure 1 As shown, the present invention provides an apparatus including a first housing 7, a gas phase product outlet 3 and a solid-liquid product outlet 4 surrounding a defined reaction chamber and communicating with the reaction chamber, wherein the gas phase outlet 3 is located at the top of the reaction chamber and the solid-liquid product outlet 4 is located at the bottom of the reaction chamber.

[0062] The reaction chamber includes a material distribution section. The chamber wall of the material distribution section is provided with a plurality of first nozzle rings and a plurality of second nozzle rings that are equally spaced along the axial direction. The first nozzle rings and second nozzle rings are arranged alternately to facilitate full contact of the material.

[0063] Each first nozzle ring includes a plurality of first nozzles 11a arranged in a ring at equal intervals along the circumference, the first nozzles 11a being used to feed the first raw material in a jet state;

[0064] Each second nozzle ring includes a plurality of second nozzles 11b arranged in a ring at equal intervals along the circumference, the second nozzles 11b being used to feed the second raw material in a jet state.

[0065] In existing technologies, the premixing of reactants in traditional reactors is uneven, or additional mixers are required, increasing design difficulty and construction costs. This invention, through the convective atomization spray design of multiple first nozzles and multiple second nozzles, can achieve thorough mixing of reactants. When using supercritical water oxidation reaction to treat organic waste liquid, it can achieve efficient removal of organic matter from organic waste liquid and simultaneous desalination and reconcentration, while reducing salt deposition on the inner wall surface.

[0066] According to a preferred embodiment of the present invention, the material distribution section is located in the region of 1 / 3 to 2 / 3 of the reaction chamber from top to bottom. When using supercritical water oxidation to treat organic waste liquid, the aforementioned method can achieve highly efficient salt separation.

[0067] To further enhance the mixing effect of the reactants, based on the staggered arrangement of the first and second nozzle rings, the first nozzle 11a and the second nozzle 11b located at the upper part of the material distribution section are inclined downwards, while the first nozzle 11a and the second nozzle 11b located at the lower part of the material distribution section are inclined upwards. In this way, both the upper and lower nozzles spray towards the middle of the material distribution section, achieving oblique convection and further ensuring thorough mixing of the reactants. When using supercritical water oxidation to treat organic waste liquid, the multi-point spraying on the inner wall can synergistically prevent salt from depositing on the surface of the reaction chamber wall, avoiding corrosion, improving operational safety, and reducing the difficulty of material selection, equipment cost, and operating cost in reactor manufacturing.

[0068] According to a preferred embodiment of the present invention, the first nozzle 11a and the second nozzle 11b located at the upper part of the material distribution section are preferably inclined downward at 0 to 45°; more preferably, the first nozzle 11a and the second nozzle 11b located at the lower part of the material distribution section are inclined upward at 0 to 45°; and even more preferably, the first nozzle 11a and the second nozzle 11b located in the middle part of the material distribution section are horizontally arranged. This concentrates the spray intersection of the upper and lower nozzles in the middle, enabling the supercritical reaction zone to be stabilized near the central axis of the reaction chamber when using supercritical water oxidation to treat organic waste liquid. A stable subcritical zone is formed in the reaction chamber surrounding the supercritical reaction zone, which surrounds the supercritical reaction zone and can dissolve inorganic salts, thus preventing salt deposits from adhering to the walls.

[0069] According to a preferred embodiment of the present invention, a second shell 6 is fitted over a first shell 7, and an annular gap 8 between the first shell 7 and the second shell 6 is provided with a first pipe 9 connecting each of the first nozzles 11a and a second pipe 10 connecting each of the second nozzles 11b. In this way, the heat generated by the exothermic reaction is transferred to the raw materials in the first and second pipes in the annular gap, preheating the raw materials subsequently entering the reaction chamber. Specifically, in the supercritical water oxidation reaction treating organic waste liquid, after heat exchange, the wall temperature of the reaction chamber is lower than the temperature of the supercritical reaction zone. Thus, the inorganic salts generated from the supercritical reaction zone dissolve in the subcritical zone, and even if salts adsorbed on the inner wall are present, they can be further dissolved and flow down the wall to the bottom of the reactor for discharge, thereby avoiding equipment corrosion caused by deposited salts adhering to the wall.

[0070] According to a preferred embodiment of the present invention, the first nozzle 11a and / or the second nozzle 11b of the material distribution section are distributed with a sparse upper portion and a denser lower portion. Specifically, the number of nozzles in the plurality of first nozzle rings and / or the plurality of second nozzle rings is distributed in an arithmetic progression from top to bottom. The number of nozzles in the uppermost first nozzle ring and / or the first second nozzle ring is a1, and so on downwards along the height direction, with the number of nozzles in the second first nozzle ring and / or the second second nozzle ring being a2, and so on, with the number of nozzles in the nth first nozzle ring and / or the nth second nozzle ring being a... n In some embodiments of the present invention, a n = a1 + (n-1) * 2, a1 = 4. The embodiments of the present invention illustrate the advantages of the invention by using 12 of each of the first and second nozzle rings, but the invention is not limited to this.

[0071] According to a preferred embodiment of the present invention, the outlet diameters of the first nozzle 11a and / or the second nozzle 11b in the material distribution section gradually increase from top to bottom. Specifically, the outlet diameters of the first nozzle 11a and / or the second nozzle 11b are distributed in an arithmetic progression from top to bottom. The outlet diameter of the first nozzle 11a and / or the second nozzle 11b of the first first nozzle ring located at the top is named R1, and so on downwards along the height direction. The outlet diameters of the first nozzle 11a and / or the second nozzle 11b of the second first nozzle ring are named R2... and so on, with the outlet diameters of the first nozzle 11a and / or the second nozzle 11b of the nth first nozzle ring being named R... n In some embodiments of the present invention, R n =r1+(n-1)*0.01, R1=0.1mm).

[0072] According to a preferred embodiment of the present invention, the first pipe 9 and the second pipe 10 are formed as a double spiral coil structure spirally wrapped around the first housing 7 along the axial direction. The double spiral coil structure can be configured to be tightly attached to the wall of the first housing to improve heat exchange efficiency. In order to facilitate feeding from the outside, one end of the first pipe 9 is closed and the other end extends out of the second housing 6 to form a first feed port 1. One end of the second pipe 10 is closed and the other end extends out of the second housing 6 to form a second feed port 2.

[0073] According to a preferred embodiment of the present invention, a fixing member for fixing the double helical coil structure is provided in the annular gap 8, preferably a bracket 13 located at the bottom end of the annular gap 8. In some embodiments of the present invention, the first housing 7 is made of ordinary stainless steel, and the second housing 6 is made of heat-resistant and high-pressure-resistant material. A top cover 5 is provided at the top of the first housing, and the top cover fits into the annular gap at the top. In this way, the first housing is fixed inside the second housing by the upper and lower limits of the top cover 5 and the bracket 13, and the double helical coil structure is also confined in the annular gap.

[0074] This invention can add commonly used components from the prior art as needed, such as control valves for the first feed inlet, the second feed inlet, or the solid-liquid product outlet, and temperature and pressure detection elements commonly used in the prior art in the equipment. This invention has no special requirements for these, and will not describe them in detail.

[0075] The application of the device of the present invention in a reaction is preferred in an oxidation reaction, and more preferably in a supercritical water oxidation reaction.

[0076] A second aspect of the present invention provides a method for treating organic waste liquid by supercritical water oxidation reaction, the method being carried out in the equipment of the present invention, comprising the following:

[0077] Under supercritical water oxidation conditions, organic waste liquid is injected into the reaction chamber through the first nozzle 11a, and a mixture containing a second oxidant is injected into the reaction chamber through the second nozzle 11b. The organic waste liquid and the mixture come into contact and undergo supercritical water oxidation to obtain gaseous products and solid products containing inorganic salts. As the reaction proceeds, the heat generated by the previous supercritical water oxidation reaction can provide reaction conditions for the subsequent supercritical water oxidation reaction, thereby improving energy utilization. The gaseous products obtained from the reaction rise and are discharged from the gaseous product outlet 3, while the solid products containing inorganic salts redissolve in the subcritical region to form solid-liquid products, which are discharged from the solid-liquid product outlet 4.

[0078] In this invention, organic waste liquid enters the spirally coiled first pipe 9 through the first feed inlet 1 and is sprayed into the reaction chamber through each first nozzle 11a. A mixture containing a second oxidant enters the second pipe 10 through the spirally coiled second feed inlet 2 and is sprayed into the reaction chamber through each second nozzle 11b. This continuous treatment of organic waste liquid utilizes the heat generated by the initial supercritical water oxidation reaction to preheat the subsequent feed mixture and provide the reaction conditions for the subsequent supercritical water oxidation reaction. This achieves simultaneous preheating of the cold feed and the reaction, improving treatment efficiency and energy utilization. The spray pressure and flow rate of the first and second nozzles can be adjusted according to the pressure or temperature inside the reaction chamber. The temperature and pressure measuring elements are commonly used in the prior art and are set in a conventional manner.

[0079] In this invention, the supercritical water oxidation reaction conditions include: a temperature of 380–600°C, preferably 400–550°C; and a pressure of 22–30 MPa, preferably 22–25 MPa.

[0080] According to a preferred embodiment of the present invention, the method of the present invention includes:

[0081] 1) Supercritical water oxidation reaction conditions for treating organic waste liquid are provided by the combustion of pre-combustion material. Specifically, preheated pre-combustion material is introduced into each first nozzle 11a, and preheated first oxidant is introduced into each second nozzle 11b. The first oxidant and pre-combustion material combust and release heat in the reaction chamber to form a supercritical reaction zone 12 that can provide supercritical water oxidation reaction conditions for step 2).

[0082] The supercritical reaction zone 12 is surrounded by a subcritical zone with a lower temperature, which is used to dissolve the inorganic salts produced by the supercritical oxidation reaction.

[0083] 2) Supercritical water oxidation reaction is used to treat organic waste liquid: the pre-combustion material introduced into the first nozzle 11a is replaced with organic waste liquid, and the first oxidant introduced into the second nozzle 11b is replaced with a mixture containing a second oxidant. The organic waste liquid and the mixture come into contact in the supercritical reaction zone 13 to undergo supercritical water oxidation reaction to obtain gaseous products and solid products containing inorganic salts.

[0084] The gaseous products generated in the reaction rise and are discharged from the gaseous product outlet 3, while the solid products containing inorganic salts are redissolved in the subcritical region to form solid-liquid products, which are discharged from the solid-liquid product outlet 4.

[0085] While achieving supercritical treatment of reactants, it can effectively utilize the heat released by the oxidation of organic matter in the reactants to heat and oxidize the raw materials that subsequently enter the reactor.

[0086] In this invention, the pre-combustion material and the organic waste liquid enter the first pipeline 9 through the first feed inlet 1 and are sprayed into the reaction chamber through each of the first nozzles 11a.

[0087] In this invention, the first oxidant and the mixture containing the second oxidant enter the second pipe 10 through the second feed port 2 and are sprayed into the reaction chamber through each of the second nozzles 11b.

[0088] In this invention, the preheating temperature of the pre-combustion material is 350–370°C.

[0089] In this invention, the preheating temperature of the first oxidant is 20–370°C.

[0090] To improve the degradation effect of organic matter and reduce operating conditions, in this invention, the supercritical water oxidation reaction is carried out in the presence of a catalyst, which is selected from homogeneous catalysts and / or heterogeneous catalysts.

[0091] In this invention, preferably, the homogeneous catalyst is selected from one or more of sodium hydroxide, soluble transition metal salts, basic salts, and heteropolyacids.

[0092] In this invention, more preferably, the soluble transition metal salt includes nitrates and / or sulfates, and the soluble transition metal salt includes at least one of Cu, Fe, Mn, Ni and Co.

[0093] In this invention, more preferably, the alkaline salt includes sodium carbonate and / or sodium bicarbonate.

[0094] In this invention, more preferably, the heteropolyacid includes at least one of phosphotungstic acid, silicotungstic acid, or phosphomolybdic acid.

[0095] According to a preferred embodiment of the present invention, the active component of the heterogeneous catalyst is selected from one or more of noble metal elements, activated carbon, and metal oxides.

[0096] In this invention, preferably, the noble metal element includes at least one of Pt, Pd, Rh, Ru and Ag.

[0097] In this invention, preferably, the metal oxide includes one or more of MgO, NiO, MnO2 and Cr2O3.

[0098] In this invention, the supported catalyst includes CeO2-ZrO2 or MnO2-ZrO2.

[0099] In this invention, the pre-combustion material is selected from at least one of methanol aqueous solution, ethanol aqueous solution, or isopropanol aqueous solution. The embodiments of this invention use a pre-combustion material with a COD of 20000 mg / L as an example to illustrate the advantages of the invention, but the invention is not limited thereto.

[0100] In this invention, the organic waste liquid comes from coal chemical or petrochemical sources.

[0101] In this invention, the organic waste liquid is selected from one or more of the following: high-concentration organic wastewater, high-salt organic wastewater, or mixed-salt organic mother liquor.

[0102] In this invention, the COD content of the high-concentration organic wastewater is ≥5000mg / L.

[0103] In this invention, the salt content (TDS) of the high-salt organic wastewater is ≥5000 mg / L.

[0104] In this invention, the main components of the organic wastewater include compounds such as phenols, pyridines, quinolines, benzenes and their derivatives.

[0105] In this invention, the first oxidant is selected from hydrogen peroxide or oxygen.

[0106] In this invention, the second oxidant is selected from one or more of air, oxygen and hydrogen peroxide.

[0107] In this invention, the mixture also includes a combustion aid and a regulator. The regulator keeps the pH value of the resulting wastewater at around 7, and the mass fraction of organic matter in the regulated wastewater is maintained at 2-3%, so that the heat released by combustion can achieve self-heating of the system.

[0108] In this invention, preferably, the combustion aid includes a combustion-supporting organic solvent; more preferably, the combustion-supporting organic solvent is selected from at least one of ethanol, isopropanol, or methanol.

[0109] In this invention, the regulator is selected from water, alkaline solution or acidic solution. The alkaline solution is a commonly used alkaline aqueous solution, such as NaOH; the acidic solution is a commonly used acidic aqueous solution, such as HCl. This invention has no special requirements for this and will not be described in detail.

[0110] According to the present invention, it is understood that during the supercritical water oxidation reaction of the present invention, the reaction is an exothermic reaction, that is, the supercritical reaction zone is formed by exothermic reaction. As the reaction proceeds, the temperature of the reaction system will continuously increase in the early stage of the reaction until the supercritical reaction zone is formed stably. The area outside the supercritical reaction zone in the reaction chamber is the subcritical zone. Those skilled in the art can control the reaction temperature to 380-600°C using conventional technical means in the art, which will not be elaborated here.

[0111] The advantages of the present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0112] Example 1

[0113] like Figure 1 As shown, a pre-combustion ethanol aqueous solution with a COD of approximately 20,000 mg / L, preheated to 350°C, enters the first pipe 9 of the double spiral coil structure located in the annular gap 8 between the first shell 7 and the second shell 6 through the first inlet 1; simultaneously, a first oxidant hydrogen peroxide aqueous solution preheated to 350°C enters the second pipe 10 of the double spiral coil structure through the second inlet 2, with an inlet pressure of 22-25 MPa.

[0114] The pre-combustion material and the first oxidant are respectively sprayed through the first nozzle 11a and the second nozzle 11b in a convective cross-spraying contact, undergoing a supercritical water oxidation reaction in the reaction chamber, releasing heat to form a supercritical reaction zone 12. The temperature is controlled at 450-550℃ and the pressure at 22-25 MPa. The first nozzle on the first pipe 9 and the second nozzle 11b on the second pipe 10 are both distributed with a sparse upper portion and a denser lower portion. Each of the first nozzle ring and the second nozzle ring has 12 nozzles. The number of first nozzles in the uppermost first nozzle ring and the number of second nozzles in the uppermost second nozzle ring are both a1 (4 nozzles), the number of first nozzles in the second first nozzle ring and the number of second nozzles in the second second nozzle ring are both a2 (6 nozzles), and so on. And so on; the outlet diameters of the first nozzle and the second nozzle gradually increase from top to bottom. Specifically, the outlet diameters of the first nozzle 11a in the uppermost first nozzle ring and the second nozzle 11b in the uppermost second nozzle ring are both R1, which is 0.1 mm. The outlet diameters of the first nozzle 11a in the second first nozzle ring and the second nozzle 11b in the second second nozzle ring are both R2, which is 0.11 mm, and so on. The first nozzle 11a and the second nozzle 11b located in the upper part of the material distribution section are inclined downward at 30°. The first nozzle and the second nozzle located in the lower part of the material distribution section are inclined upward at 30°. The first nozzle and the second nozzle located in the middle part of the material distribution section are horizontally positioned.

[0115] The reactants in the first pipeline 9 were switched to organic wastewater (COD) from catalyst production at a petrochemical company. Cr The first pipe (5000 mg / L, TDS 10000 mg / L) is replaced with a mixture containing a second oxidant (hydrogen peroxide solution), a combustion aid (isopropanol solution), and a regulator (sodium bicarbonate solution, adjusted to maintain the pH of the resulting high-concentration wastewater at around 7 and the mass fraction of organic matter at around 3%). The organic wastewater and the mixture are respectively sprayed into the supercritical reaction zone 12 through the first nozzle 11a and the second nozzle 11b in a convective cross-flow manner. After further mixing and enhancement, a supercritical exothermic oxidation reaction occurs, forming gaseous reaction products and solid-liquid products. The gaseous products and water vapor rise to the gaseous product outlet 3 and are discharged. The solid products redissolve in the subcritical zone of the reaction chamber, forming a concentrated salt liquid product, which is discharged from the lower solid-liquid product outlet 4. In this embodiment, the catalyst is sodium hydroxide.

[0116] The final treatment result is that the TDS content in the condensate (referring to the demineralized water with COD basically removed) after condensation of the gas phase outlet product is 10 mg / L, and the chemical oxygen demand (COD) is... Cr The concentration was 0 mg / L, and the TDS of the concentrated brine at the bottom solid-liquid product outlet was 150,000 mg / L, COD... Cr Content 0 mg / L.

[0117] Example 2

[0118] like Figure 1 As shown, a pre-combustion methanol aqueous solution with a COD of 20000 mg / L, preheated to 360°C, enters the first pipe 9 of the double spiral coil structure located in the annular gap 8 between the first shell 7 and the second shell 6 through the first inlet 1; at the same time, a first oxidant hydrogen peroxide aqueous solution preheated to 360°C enters the second pipe 10 of the double spiral coil structure through the second inlet 2, with an inlet pressure of 22-25 MPa.

[0119] Methanol-water solution and hydrogen peroxide-water solution are respectively sprayed through a first nozzle 11a and a second nozzle 11b in a convective cross-jet contact, undergoing a supercritical water oxidation reaction in the reaction chamber, releasing heat to form a supercritical reaction zone 12. The temperature is controlled at 450-550℃ and the pressure at 22-25 MPa. The first nozzle on the first pipe 9 and the second nozzle 11b on the second pipe 10 are both distributed with a sparse upper portion and a denser lower portion. There are 12 nozzle rings in each of the first and second nozzle rings. The number of first nozzles in the uppermost first nozzle ring and the number of second nozzles in the uppermost second nozzle ring are both a1, which is 4. The number of first nozzles in the second first nozzle ring and the number of second nozzles in the second second nozzle ring are both a2, which is 6. And so on; and the outlet diameters of the first nozzle and the second nozzle gradually increase from top to bottom. Among them, the outlet diameters of the first nozzle 11a in the first first nozzle ring and the second nozzle 11b in the first second nozzle ring at the top are both R1 = 0.1mm, the outlet diameters of the first nozzle 11a in the second first nozzle ring and the second nozzle 11b in the second second nozzle ring are both R2 = 0.11mm, and so on; the first nozzle 11a and the second nozzle 11b located in the upper part of the material distribution section are inclined downward at 15°; the first nozzle and the second nozzle located in the lower part of the material distribution section are inclined upward at 15°; the first nozzle and the second nozzle located in the middle of the material distribution section are horizontally arranged.

[0120] The reactant in the first pipeline 9 was switched to ethylene alkali residue wastewater (COD) from a petrochemical enterprise. CrThe concentration of the wastewater is 10000 mg / L, and the TDS is 25000 mg / L. The second pipe 10 is replaced with a mixture containing oxygen as the second oxidant, isopropanol solution as the combustion aid, and HCl as the regulator (adjusted to maintain the pH of the resulting high-concentration salt wastewater at around 7 and the mass fraction of organic matter at around 3%). The organic wastewater and the mixture are respectively sprayed into the supercritical reaction zone 12 through the first nozzle 11a and the second nozzle 11b in a cross-convection manner. After further mixing and enhancement, a supercritical exothermic oxidation reaction is carried out to form gaseous reaction products and solid-liquid products. The gaseous products after the reaction rise to the gaseous product outlet 3 and are discharged. The solid products after the reaction redissolve in the subcritical zone of the reaction chamber to form a concentrated salt liquid product, which is discharged from the lower solid-liquid product outlet 4. In this embodiment, the heterogeneous catalyst active component is Pt.

[0121] The final treatment result is that the TDS content in the condensate (referring to the demineralized water with COD basically removed) after condensation of the gas phase outlet product is 10 mg / L, and the chemical oxygen demand (COD) is... Cr The concentration was 0 mg / L, and the TDS of the concentrated brine at the bottom solid-liquid product outlet was 200,000 mg / L, COD... Cr The content is 0 mg / L.

[0122] Example 3

[0123] like Figure 1 As shown, a pre-combustion ethanol aqueous solution with a COD of 20000 mg / L, preheated to 370°C, is introduced into the first pipe 9 of the double spiral coil structure located in the annular gap 8 between the first shell 7 and the second shell 6 through the first inlet 1; at the same time, the first oxidant oxygen, preheated to 370°C, is introduced into the second pipe 10 of the double spiral coil structure through the second inlet 2, with an inlet pressure of 22-25 MPa.

[0124] Ethanol-water solution and oxygen are respectively injected through a first nozzle 11a and a second nozzle 11b in a convective cross-jet contact, undergoing a supercritical water oxidation reaction in the reaction chamber, releasing heat to form a supercritical reaction zone 12. The temperature is controlled at 450-550℃ and the pressure at 22-25 MPa. The first nozzle on the first pipe 9 and the second nozzle 11b on the second pipe 10 are both distributed with a sparser upper section and a denser lower section. Each of the first and second nozzle rings has 12 nozzles. The number of first nozzles in the uppermost first nozzle ring and the number of second nozzles in the uppermost second nozzle ring are both a1 (4 nozzles), the number of first nozzles in the second first nozzle ring and the number of second nozzles in the second second nozzle ring are both a2 (6 nozzles), and so on. And so on; the outlet diameters of the first nozzle and the second nozzle gradually increase from top to bottom. Specifically, the outlet diameters of the first nozzle 11a in the first first nozzle ring and the second nozzle 11b in the first second nozzle ring at the top are both R1, which is 0.1 mm. The outlet diameters of the first nozzle 11a in the second first nozzle ring and the second nozzle 11b in the second second nozzle ring are both R2, which is 0.11 mm, and so on. The first nozzle 11a and the second nozzle 11b located at the upper part of the material distribution section are inclined downward at 45°. The first nozzle and the second nozzle located at the lower part of the material distribution section are inclined upward at 45°. The first nozzle and the second nozzle located in the middle of the material distribution section are horizontally positioned.

[0125] The reactant in the first pipeline 9 was switched to a mother liquor (COD) from the final stage of water treatment at a coal chemical plant, which was converted from a mixed salt evaporation solution. Cr The concentration of the wastewater was 20,000 mg / L, and the TDS was 50,000 mg / L. The second pipe 10 was replaced with a mixture containing air as a second oxidant, methanol solution as a combustion aid, and sodium bicarbonate solution as a regulator (adjusted to maintain the pH of the resulting high-concentration salt wastewater at around 7 and the mass fraction of organic matter at around 3%). The organic wastewater and the mixture were each injected into the supercritical reaction zone 12 through a cross-flow convection jet from the first nozzle 11a and the second nozzle 11b. After further mixing and enhancement, a supercritical exothermic oxidation reaction was carried out, forming gaseous reaction products and solid-liquid products. The gaseous products after the reaction rose to the gaseous product outlet 3 and were discharged. The solid products after the reaction redissolved in the subcritical zone of the reaction chamber, forming a concentrated salt liquid product, which was discharged from the lower solid-liquid product outlet 4. In this embodiment, the active component of the heterogeneous catalyst is MgO.

[0126] The final treatment result is that the TDS content in the condensate (referring to the demineralized water with COD basically removed) after condensation of the gas phase outlet product is 10 mg / L, and the chemical oxygen demand (COD) is... Cr The concentration was 0 mg / L, and the TDS of the concentrated brine at the bottom solid-liquid product outlet was 250,000 mg / L, COD... Cr The content is 0 mg / L.

[0127] Example 4

[0128] Unlike Example 1, the first nozzle 11a and the second nozzle 11b located in the material distribution section are both horizontally arranged.

[0129] The final treatment result is that the TDS content in the condensate (referring to the demineralized water with essentially COD removed) after condensation of the gas phase outlet product is 200 mg / L, and the chemical oxygen demand (COD) is... Cr The concentration was 300 mg / L, and the TDS concentration of the concentrated brine at the bottom solid-liquid product outlet was 50,000 mg / L, COD... Cr The content is 500 mg / L.

[0130] Example 5

[0131] Unlike Example 1, the first nozzle 11a and the second nozzle 11b in the material distribution section are equidistant from top to bottom; the outlet diameters of the first nozzle 11a and the second nozzle 11b in the material distribution section are the same.

[0132] The final treatment result is that the TDS content in the condensate (referring to the demineralized water with essentially COD removed) after condensation of the gas phase outlet product is 100 mg / L, and the chemical oxygen demand (COD) is [not specified]. Cr The concentration was 200 mg / L, and the TDS concentration of the concentrated brine at the bottom solid-liquid product outlet was 40,000 mg / L, COD... Cr The content is 400 mg / L.

[0133] Comparative Example 1

[0134] CN110963557A discloses a saline wastewater treatment system and method, which uses a conventional tubular reactor. Example 2 shows that after treatment, saline wastewater with a TDS of 30,000 mg / L and a COD of 1,000 mg / L has a final TDS of 200,000 mg / L and a COD of [missing information - likely related to a specific chemical formula or specification]. Cr The content is 0 mg / L.

[0135] The comparison shows that the COD concentration of the treated wastewater is lower, and the salt concentration rate is also lower (only 6.67 times concentrated).

[0136] This invention enables efficient degradation of COD in high-concentration organic waste liquid and simultaneous salt concentration, achieving reduction, harmlessness and resource utilization of high-concentration organic waste liquid, effectively preventing salt deposition and blockage, improving operational safety, and reducing equipment cost and operating cost.

[0137] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An apparatus for supercritical water oxidation reaction, characterized in that, Includes a first housing (7), a reaction chamber defined by the first housing (7), and a gaseous product outlet (3) and a solid-liquid product outlet (4) communicating with the reaction chamber. The reaction chamber includes a material distribution section, and the chamber wall of the material distribution section is provided with a plurality of first nozzle rings and a plurality of second nozzle rings that are sequentially spaced along the axial direction, and the first nozzle rings and second nozzle rings are arranged alternately. Each of the first nozzle rings includes a plurality of first nozzles (11a) arranged in a ring shape at circumferential intervals, the first nozzles (11a) being used to feed a first raw material; Each of the second nozzle rings includes a plurality of second nozzles (11b) arranged in a ring at circumferential intervals, the second nozzles (11b) being used to feed a second raw material; The first nozzle (11a) and the second nozzle (11b) located at the upper part of the material distribution section are inclined downward at 0~45°; The first nozzle (11a) and the second nozzle (11b) located at the lower part of the material distribution section are inclined upward at 0~45°; The first nozzle (11a) and the second nozzle (11b) located in the middle of the material distribution section are horizontally arranged; The first nozzle (11a) and the second nozzle (11b) of the material distribution section are distributed with sparser nozzles at the top and denser nozzles at the bottom. The outlet diameters of the first nozzle (11a) and the second nozzle (11b) in the material distribution section gradually increase from top to bottom; The first housing (7) is covered with a second housing (6), and the annular gap (8) between the first housing (7) and the second housing (6) is provided with a first pipe (9) connecting each of the first nozzles (11a) and a second pipe (10) connecting each of the second nozzles (11b).

2. The device according to claim 1, characterized in that, The material distribution section is located in the region of the reaction chamber, which is 1 / 3 to 2 / 3 of the way from top to bottom.

3. The device according to claim 1 or 2, characterized in that, The first pipe (9) and the second pipe (10) are formed as a double-helix coil structure spirally wound around the first housing (7) along the axial direction. One end of the first pipe (9) is closed and the other end extends out of the second housing (6) to form a first inlet (1). One end of the second pipe (10) is closed and the other end extends out of the second housing (6) to form a second inlet (2); and / or The annular gap (8) is provided with a fastener for fixing the double spiral coil structure.

4. The device according to claim 3, characterized in that, The fastener is configured as a bracket (13) located at the bottom end of the annular gap (8).

5. The application of the device according to any one of claims 1-4 in supercritical water oxidation reaction.

6. A method for treating organic waste liquid by supercritical water oxidation, characterized in that, The method is performed in the apparatus according to any one of claims 1-4, and includes: Under supercritical water oxidation reaction conditions, organic waste liquid is injected into the reaction chamber from the first nozzle (11a), and a mixture containing a second oxidant is injected into the reaction chamber from the second nozzle (11b). The organic waste liquid and the mixture come into contact and undergo supercritical water oxidation reaction to obtain gaseous products and solid products containing inorganic salts. Among them, the gaseous product rises and is discharged from the gaseous product outlet (3), and the solid product containing inorganic salts is redissolved in the subcritical region to form a solid-liquid product and is discharged from the solid-liquid product outlet (4).

7. The method according to claim 6, wherein, The organic waste liquid enters the first pipe (9) through the first inlet (1) and is sprayed into the reaction chamber through each of the first nozzles (11a); and / or The mixture containing the second oxidant enters the second pipe (10) through the second inlet (2) and is sprayed into the reaction chamber through each of the second nozzles (11b); and / or The supercritical water oxidation reaction conditions include: a temperature of 380~600℃ and a pressure of 22~30 MPa.

8. The method according to claim 7, wherein, The supercritical water oxidation reaction conditions include: a temperature of 400~550℃ and a pressure of 22~25 MPa.

9. The method according to claim 6, wherein, The method includes: 1) Provide supercritical water oxidation reaction conditions through the combustion of pre-combustion material: preheated pre-combustion material is introduced into each first nozzle (11a), and preheated first oxidant is introduced into each second nozzle (11b). The first oxidant and pre-combustion material combust and release heat in the reaction chamber to form a supercritical reaction zone (12) that can provide supercritical water oxidation reaction conditions for step 2). The supercritical reaction zone (12) is surrounded by a subcritical zone with a lower temperature, which is used to dissolve the inorganic salts produced by the supercritical oxidation reaction. 2) Supercritical water oxidation reaction: The pre-combustion material introduced into the first nozzle (11a) is switched to organic waste liquid, and the first oxidant introduced into the second nozzle (11b) is converted into a mixture containing a second oxidant. The organic waste liquid and the mixture come into contact in the supercritical reaction zone (12) to undergo supercritical water oxidation reaction.

10. The method according to claim 9, wherein, The pre-combustion material and the organic waste liquid enter the first pipeline (9) through the first inlet (1) and are sprayed into the reaction chamber through each of the first nozzles (11a); and / or The first oxidant and the mixture containing the second oxidant enter the second pipe (10) through the second inlet (2) and are sprayed into the reaction chamber through each of the second nozzles (11b); and / or The preheating temperature of the pre-combustion material is 350~370℃; and / or The preheating temperature of the first oxidant is 20~370℃.

11. The method according to any one of claims 6-10, wherein, The supercritical water oxidation reaction is carried out in the presence of a catalyst, which is selected from homogeneous catalysts and / or heterogeneous catalysts.

12. The method according to claim 11, wherein, The homogeneous catalyst is selected from one or more of sodium hydroxide, soluble transition metal salts, basic salts, and heteropolyacids.

13. The method according to claim 12, wherein, The soluble transition metal salt includes nitrates and / or sulfates, and the soluble transition metal salt comprises at least one of Cu, Fe, Mn, Ni, and Co; and / or The alkaline salt includes sodium carbonate and / or sodium bicarbonate; and / or The heteropolyacids include at least one of phosphotungstic acid, silicotungstic acid, and phosphomolybdic acid.

14. The method according to claim 11, wherein, The active components of the heterogeneous catalyst include one or more of noble metal elements, activated carbon, and metal oxides.

15. The method according to claim 14, wherein, The noble metal element includes at least one of Pt, Pd, Rh, Ru, and Ag; and / or The metal oxide includes one or more of MgO, NiO, MnO2, and Cr2O3.

16. The method according to claim 9, wherein, The pre-combustion material is selected from at least one of methanol aqueous solution, ethanol aqueous solution, or isopropanol aqueous solution; and / or The organic waste liquid originates from coal chemical or petrochemical industries; and / or The organic waste liquid is selected from one or more of the following: high-concentration organic wastewater, high-salt organic wastewater, and mixed-salt organic mother liquor; and / or The first oxidant is selected from hydrogen peroxide or oxygen; and / or The second oxidant is selected from one or more of air, oxygen and hydrogen peroxide.

17. The method according to claim 16, wherein, The mixture also includes combustion improvers and modifiers.

18. The method according to claim 17, wherein, The regulator is selected from water, an alkaline solution, or an acidic solution; and / or The combustion aid includes combustion-supporting organic solvents.

19. The method according to claim 18, wherein, The combustion-supporting organic solvent is selected from at least one of ethanol, isopropanol, or methanol.

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