CN111762866A - Multifunctional supercritical water enhanced oxidation system for refractory nitrogenous and high-salinity organic pollutants - Google Patents
Multifunctional supercritical water enhanced oxidation system for refractory nitrogenous and high-salinity organic pollutants Download PDFInfo
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Abstract
The invention relates to a multifunctional supercritical water enhanced oxidation system for nitrogen-containing and high-salt organic pollutants difficult to degrade, which comprises an oxidant pretreatment unit, a material pretreatment unit, a medicament pretreatment unit, a supercritical water oxidation unit, a water supply unit and a product subsequent treatment unit. Multiple intensified oxidation technologies such as reactor inner wall surface catalysis, heterogeneous metal oxide catalysis, auxiliary agent co-oxidation, segmented co-oxidation, inorganic salt catalytic oxidation and the like are coupled in a supercritical water oxidation system at one time, and the combination of one or more intensified technologies can realize the synergistic efficient removal of nitrogen-containing organic pollutants COD and ammonia nitrogen under relatively mild reaction conditions, so that the system operation conditions and the equipment investment cost are reduced, and the system economy and the safety reliability are improved. Meanwhile, salt crystallization, deposition and blockage of the preheater, the heater and other devices and connecting pipelines thereof in the preheating process are avoided, and the operation reliability of the system is improved.
Description
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to a multifunctional supercritical water enhanced oxidation system and method for refractory nitrogen-containing and high-salt organic pollutants.
Background
The rapid development of economy brings a serious environmental pollution problem, the annual emission of high-concentration refractory organic wastewater and sludge is continuously increased, in 2016, the emission of industrial wastewater exceeds 200 hundred million tons, and the emission of municipal sludge exceeds 4000 million tons, so that the safety of ecological environment and the health of human beings are seriously influenced. It is worth noting that the wastewater generated in the chemical, petrochemical, pharmaceutical, petroleum, printing and dyeing industries contains a large amount of nitrogen-containing organic matters, such as sulfonamides and quinolone antibiotics in medical wastewater, pyridine, quinoline and furan in pesticide wastewater, pyridine, indole and amide in coking wastewater, pyridine, aniline and nitrobenzene in printing and dyeing wastewater. Further, municipal sewage and municipal sludge contain a large amount of nitrogen-containing compounds such as proteins and amino acids. In the process of treating wastewater and sludge, nitrogen-containing compounds are always pollutants strictly controlled by the state, most nitrogen-containing organic matters have toxicity, particularly, the nitrogen-containing organic matters can cause cancers when being contacted with human blood systems and nervous systems for a long time, and can also cause acute poisoning and even death of human bodies, so that the nitrogen-containing organic wastes can be discharged after being properly treated.
The methods commonly used for degrading nitrogenous organic waste at present mainly comprise a physicochemical method, a biochemical method and an advanced oxidation method. The physical and chemical method is generally only suitable for low-concentration nitrogen-containing organic wastewater and is generally used as pretreatment of other methods. Because of high toxicity and poor biodegradability of nitrogen-containing organic matters, microorganisms are easy to be poisoned, and the application of a biochemical method is limited to a certain extent. The conventional advanced oxidation techniques such as chemical oxidation and wet oxidation have the disadvantages of low treatment efficiency, long operation time, high treatment cost, and the generation of more toxic by-products. In addition, although the incineration method can reduce the volume and the amount of the nitrogen-containing organic hazardous wastes to a certain extent, secondary pollution such as NOx is easily generated in the incineration process of organic matters containing nitrogen and heteroatoms, the generated fly ash containing heavy metal ions needs to be further buried, harmful components cannot be fundamentally destroyed by the burying, and the generated landfill leachate seriously pollutes surface water and underground water.
Supercritical water oxidation (SCWO) was proposed by professor Modell of the institute of technology, Massachusetts, 80 s in the last century and is a novel organic waste treatment technology. By utilizing the special properties of low dielectric constant, low viscosity, high diffusivity and the like of water in a supercritical state (the temperature is more than 374.1 ℃ and the pressure is more than 22.1MPa), supercritical water is used as a reaction medium, so that organic matters and oxygen are completely dissolved in the supercritical water and a homogeneous, rapid and efficient oxidation reaction is carried out, and C, H elements in the organic matters are respectively converted into harmless CO2、H2O small molecular substance, heterocyclic atoms such as Cl, S and P, etc. are respectively converted into corresponding inorganic acid or salt, and heavy metal is mineralized into stable solid phase and exists in the residue. Compared with the traditional technology, the method has the technical advantages of rapidness (less than 2min), high efficiency (removal rate more than 99%), no secondary pollution, capability of realizing system self-heating, high economy and the like.
However, when supercritical water oxidation technology is used for treating nitrogen-containing and high-salt organic pollutants which are difficult to degrade, some problems exist:
(1) under typical SCWO reaction conditions (400-600 ℃, 24-28 MPa), although the COD removal rate of the nitrogenous organic matters can reach more than 99%, most of organic nitrogen is converted into intermediate product ammonia nitrogen, and the further degradation of the ammonia nitrogen is a rate determining step in the SCWO process of the nitrogenous organic matters although the structure of the ammonia nitrogen is simple. A large number of researchers show that ammonia nitrogen cannot be oxidized when the temperature is lower than 525 ℃, and even if the reaction temperature is increased to 650 ℃, the removal rate of ammonia nitrogen is only 10.9%. In order to further realize effective degradation of ammonia nitrogen, higher reaction temperature (higher than 650 ℃), higher reaction pressure (27-30 MPa) and longer residence time (longer than 10min) are required, the reaction conditions are extremely harsh, the high-temperature and high-pressure reaction environment undoubtedly increases the performance requirements on high-temperature resistance and corrosion resistance of reactor materials, the long residence time also further increases the size of the reactor, and if a subsequent ammonia distillation treatment process is combined, the equipment investment of an SCWO reaction system is undoubtedly further increased, so that the economical efficiency and the safety and reliability of the whole system are reduced.
(2) When organic pollutant solution containing inorganic salt ions is treated, SO is generated due to the special properties of small dielectric constant of supercritical water and low solubility to inorganic salt2 -、Cl-In the preheating process, especially in tubular equipment such as a preheater and an electric heater (at the moment, supercritical water is converted from a subcritical state to a supercritical state), inorganic salt ions are easy to crystallize, precipitate and deposit on the wall surface of a pipeline, and finally the blockage of the equipment such as the preheater and the electric heater and connecting pipelines thereof is caused, so that the normal operation of the SCWO system is influenced, and even the complete breakdown and shutdown of the system are caused.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a multifunctional supercritical water enhanced oxidation system and a multifunctional supercritical water enhanced oxidation method for refractory nitrogen-containing and high-salt organic pollutants, which can effectively solve the technical problem that ammonia nitrogen as a refractory intermediate product is difficult to be removed completely in cooperation with COD under relatively mild reaction conditions when the supercritical water oxidation technology is used for treating the nitrogen-containing organic pollutants, and realize that the COD and the ammonia nitrogen after the treatment of the nitrogen-containing organic pollutants reach the standard once and are directly discharged.
In order to achieve the purpose, the invention adopts the technical scheme that:
a multi-functional supercritical water enhanced oxidation system for refractory nitrogen-containing and high-salinity organic pollutants, comprising:
a supercritical water oxidation unit comprising a supercritical water oxidation reactor 14;
the system comprises an oxidant pretreatment unit and a supercritical water oxidation reactor, wherein the oxidant pretreatment unit is divided into two paths, one path comprises a liquid oxygen storage tank 1, a high-pressure liquid oxygen pump 2, a liquid oxygen gasifier 3 and an oxygen buffer tank 4 which are sequentially communicated, the other path comprises a hydrogen peroxide storage tank 6, a hydrogen peroxide high-pressure pump 7 and a hydrogen peroxide heater 8 which are sequentially communicated, an outlet of the hydrogen peroxide heater 8 is connected with an outlet of the oxygen buffer tank 4, the two paths are divided into two paths through an oxidant proportion distribution meter 5 after being connected, one path is directly connected with an oxidant inlet of an end cover of the supercritical water oxidation reactor 14, and the other path is connected with each segmented oxygen inlet on the side surface of the supercritical;
the material pretreatment unit comprises a material preparation tank 9, a material high-pressure pump 10, a preheater 11, a material heater 12 and a material mixer 13 which are sequentially communicated, wherein the outer pipe of the preheater 11 is positioned on a communicating pipeline, and the outlet of the material mixer 13 is connected with the material inlet of a supercritical water oxidation reactor 14;
the reagent pretreatment unit comprises a reagent preparation tank 18, a reagent high-pressure pump 19 and a reagent heater 20 which are sequentially communicated, wherein the outlet of the reagent heater 20 is divided into two paths, one path is connected with the inlet of the material mixer 13, the other path is divided into two paths through a reagent proportion distribution meter 21, one path is directly connected with the reagent inlet of the end cover of the supercritical water oxidation reactor 14, and the other path is connected with each sectional reagent inlet on the side surface of the supercritical water oxidation reactor 14;
the product subsequent treatment unit comprises a steam generator 15, a pressure reduction device 16 and a product separator 17 which are sequentially communicated, wherein an outlet of the supercritical water oxidation reactor 14 is connected with an inlet of an inner pipe of the material preheater 11, an outlet of an inner pipe of the material preheater 11 is connected with an inlet of an outer pipe of the steam generator 15, an outlet of an outer pipe of the steam generator 15 is connected with an inlet of the pressure reduction device 16, and an outlet of the pressure reduction device 16 is connected with an inlet of the product separator 17;
the water supply unit comprises a water storage tank 22, a water pump 23 and a steam storage tank 24 which are sequentially communicated, wherein the outlet of the water pump 23 is divided into two paths, one path of outlet is connected with the inlet of an inner tube of the steam generator 15, the outlet of the inner tube of the steam generator 15 is connected with the inlet of the steam storage tank 24, and the other path of outlet is directly connected with the cooling water inlet of the supercritical water oxidation reactor 14.
Preferably, the hydrogen peroxide storage tank 6 includes a shading and cooling device outside, the material blending tank 9 and the chemical blending tank 18 are provided with mixers, the mixers are frame mixers, paddle mixers, turbine mixers or ribbon mixers, the preheater 11 and the steam generator 15 are sleeve-type heat exchangers or shell-and-tube heat exchangers, the hydrogen peroxide heater 8, the material heater 12 and the chemical heater 20 are electric heaters, electromagnetic induction heaters, natural gas furnace heaters or diesel oil heaters, the material mixer 13 is a venturi mixer, a T-type mixer or a flute-type tubular mixer, the pressure reduction device 16 is a capillary tube pressure reducer, a back pressure valve, a pressure regulating valve or a multi-stage valve step-by-step pressure reduction device, the product separator 17 is a gas-liquid separator or a gas-liquid-solid three-phase separator, the outer side of the upper portion of the supercritical water oxidation reactor 14 is provided with a heater, the heater is an electric heater or an electromagnetic induction heater.
Preferably, the oxidant proportioner 5, the two main paths of the medicament proportioner 21 and the distributed branches are all provided with precise flow meters.
Preferably, the medicament in the medicament reservoir 18 is one or more of alcohols, nitrates or nitrites.
Preferably, the alcohol is methanol, ethanol, ethylene glycol or isopropanol, the nitrate salt is sodium nitrate, potassium nitrate or lithium nitrate, and the nitrite salt is sodium nitrite.
Preferably, the inner wall surface of the supercritical water oxidation reactor 14 is provided with a replaceable liner, the material of the liner is titanium or nickel, the outer side of the liner is provided with an oxidant spiral channel, the outer side of the oxidant spiral channel is provided with a cooling water spiral channel, and the spiral channel is a single spiral channel or a double spiral channel.
Preferably, a detachable packed bed catalyst is arranged inside the supercritical water oxidation reactor 14, and a flow equalizing plate is arranged on the upper part of the packed bed catalyst.
Preferably, a heat insulation and preservation channel is arranged between the material channel and the oxidant channel of the supercritical water oxidation reactor 14, a heat insulation material is filled in the heat insulation channel, a spiral atomizing nozzle is installed at the outlet of the material channel, and an internal thread screwing device is arranged at the outlet of the oxidant channel and the outlet of the medicament channel.
Preferably, the side surface of the supercritical water oxidation reactor 14 is provided with 4 segmented oxygen inlet channels and segmented chemical inlet channels from top to bottom, and outlets of contact positions of the segmented oxygen inlet channels and the segmented chemical inlet channels and the inner wall surface lining are provided with a plurality of downward inclined annular holes.
Preferably, 5 thermocouple temperature measuring points are arranged on the upper and lower sides of the side surface of the supercritical water oxidation reactor 14, the first temperature measuring point is located on the reaction initial plane, the rest temperature measuring points are respectively located behind the segmented oxygen inlet positions, and a pressure measuring point is arranged at the end cover of the reactor.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines various supercritical water enhanced oxidation technologies at one time, including reactor inner wall surface catalysis, heterogeneous metal oxide catalysis, auxiliary agent co-oxidation, sectional co-oxidation and inorganic salt catalytic oxidation, any enhanced oxidation technology or coupling of two or more technologies can realize synergistic efficient degradation and standard emission of COD and ammonia nitrogen at one time under relatively mild supercritical reaction conditions (450-600 ℃, 24-25 MPa and 10-60 s), the size of the reactor is reduced, the requirements on high temperature and high pressure resistance and corrosion resistance of reactor materials are properly reduced, a subsequent treatment module for ammonia nitrogen is omitted, the investment of system equipment is reduced from the source, and the economy of the system is improved.
2. The specially designed supercritical water oxidation reactor, the spiral atomizing nozzle arranged at the material channel outlet and the internal thread swirling device arranged at the oxidant and auxiliary agent channel outlet can strengthen the mixing of the material, the oxidant and the auxiliary agent, thereby strengthening the supercritical water oxidation reaction. Meanwhile, a plurality of inclined downward annular holes are formed in outlets of contact positions of the segmented oxygen inlet channel and the segmented medicine inlet channel on the reactor and the inner wall surface lining, so that oxidant and medicine can be uniformly injected on a plane, on one hand, the gathering and rising of reaction temperature in the reactor caused by oxygen injection point concentration are avoided, the corrosion hazard of high-temperature concentration to the reactor is reduced, the material requirement on the reactor is reduced, the reliability and the economical efficiency of the system are improved, on the other hand, uniform contact between auxiliary medicine, oxidant and reaction materials is strengthened, the SCWO reaction rate is accelerated, and the high efficiency of the system is improved.
3. The outer wall surface of the supercritical water oxidation reactor used in the invention is provided with a heater, when organic pollutant solution containing inorganic salt ions is treated, materials can directly enter a material channel on the end cover of the reactor in a cold material (normal temperature) state after being pressurized and are sprayed into the reactor after being atomized by a spiral atomizing nozzle, the heater on the outer wall surface of the reactor can directly heat the materials in the reactor to the supercritical temperature, if the effect of an auxiliary fuel alcohol auxiliary agent is added, the preheated materials, the alcohol auxiliary agent and an oxidant can generate supercritical water heat combustion reaction with faster reaction rate and more thorough removal efficiency in the reactor, thereby avoiding the problems of salt crystallization and deposition generated when salt-containing materials pass through a preheater and the heater due to the characteristics of low dielectric constant of supercritical water and small solubility to inorganic salt while strengthening SCWO reaction, the blockage of pipelines, preheaters, heaters and other equipment is avoided, and the safety and the reliability of the system are improved.
Drawings
FIG. 1 is a schematic view of a reaction system of the present invention.
In the figure: 1-a liquid oxygen storage tank; 2-high pressure liquid oxygen pump; 3-liquid oxygen gasifier; 4-an oxygen buffer tank; 5-oxidant proportion distributor; 6-hydrogen peroxide storage tank; 7-a high pressure hydrogen peroxide pump; 8-a hydrogen peroxide heater; 9-material blending tank; 10-material high-pressure pump; 11-a preheater; 12-a material heater; 13-material mixer; 14-supercritical water oxidation reactor; 15-a steam generator; 16-a pressure reduction device; 17-a product separator; 18-a medicament dispensing canister; 19-a medicament high pressure pump; 20-a medicament heater; 21-a medicament ratio dispenser; 22-a water storage tank; 23-a water pump; 24-steam storage tank.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Referring to fig. 1, a multifunctional supercritical water enhanced oxidation system and method for refractory nitrogen-containing and high-salt organic pollutants comprises an oxidant pretreatment unit, a material pretreatment unit, a medicament pretreatment unit, a supercritical water oxidation unit, a water supply unit and a product subsequent treatment unit.
Specifically, the method comprises the following steps:
the supercritical water oxidation unit includes a supercritical water oxidation reactor 14;
the oxidant pretreatment unit is divided into two paths, one path comprises a liquid oxygen storage tank 1, a high-pressure liquid oxygen pump 2, a liquid oxygen gasifier 3 and an oxygen buffer tank 4, the outlet of the liquid oxygen storage tank 1 is connected with the inlet of the high-pressure liquid oxygen pump 2, the outlet of the high-pressure liquid oxygen pump 2 is connected with the inlet of the liquid oxygen gasifier 3, the outlet of the liquid oxygen gasifier 3 is connected with the inlet of the oxygen buffer tank 4, the other path comprises a hydrogen peroxide storage tank 6, a hydrogen peroxide high-pressure pump 7 and a hydrogen peroxide heater 8, the outlet of the hydrogen peroxide storage tank 6 is connected with the inlet of the hydrogen peroxide high-pressure pump 7, the outlet of the hydrogen peroxide high-pressure pump 7 is connected with the inlet of the hydrogen peroxide heater 8, the outlet of the hydrogen peroxide heater 8 is connected with the outlet of the oxygen buffer tank 4, the two paths are divided into two paths through an oxidant proportion meter 5 after the two paths are connected, and the other, the other path is connected with each segmented oxygen inlet on the side surface of the supercritical water oxidation reactor 14;
the material pretreatment unit comprises a material blending tank 9, a material high-pressure pump 10, a preheater 11, a material heater 12 and a material mixer 13. The outlet of the material blending tank 9 is connected with the inlet of a material high-pressure pump 10, the outlet of the material high-pressure pump 10 is connected with the inlet of an outer tube of a preheater 11, the outlet of the outer tube of the preheater 11 is connected with the inlet of a material heater 12, the outlet of the material heater 12 is connected with the inlet of a material mixer 13, and the outlet of the material mixer 13 is connected with the material inlet of a supercritical water oxidation reactor 14;
the reagent pretreatment unit comprises a reagent preparation tank 18, a reagent high-pressure pump 19 and a reagent heater 20, wherein the outlet of the reagent preparation tank 18 is connected with the inlet of the reagent high-pressure pump 19, the outlet of the reagent high-pressure pump 19 is connected with the inlet of the reagent heater 20, the outlet of the reagent heater 20 is divided into two paths, one path is connected with the inlet of the material mixer 13, the other path is divided into two paths through a reagent proportion distribution meter 21, one path is directly connected with the reagent inlet of the end cover of the supercritical water oxidation reactor 14, and the other path is connected to each segmented reagent inlet on the side surface of the supercritical water oxidation reactor 14;
the product subsequent treatment unit comprises a steam generator 15, a pressure reduction device 16 and a product separator 17, wherein the outlet of the supercritical water oxidation reactor 14 is connected with the inlet of the inner pipe of the material preheater 11, the outlet of the inner pipe of the material preheater 11 is connected with the inlet of the outer pipe of the steam generator 15, the outlet of the outer pipe of the steam generator 15 is connected with the inlet of the pressure reduction device 16, and the outlet of the pressure reduction device 16 is connected with the inlet of the product separator 17;
the water supply unit includes water storage tank 22, water pump 23, steam storage tank 24, and the export of water storage tank 22 links to each other with water pump 23's import, and water pump 23's export is divided into two the tunnel, links to each other with steam generator 15's inner tube import all the way, and steam generator 15's inner tube export links to each other with steam storage tank 24's import, and another way is direct to link to each other with supercritical water oxidation reactor 14's cooling water entry.
The following is a further optimized structure of the invention:
the hydrogen peroxide storage tank 6 can be externally provided with a shading and cold insulation device.
The material preparation tank 9 and the medicament preparation tank 18 are internally provided with stirrers, and the stirrers can be frame stirrers, blade stirrers, turbine stirrers, ribbon stirrers and the like.
The preheater 11 and the steam generator 15 may be a double pipe heat exchanger or a shell and tube heat exchanger.
The hydrogen peroxide heater 8, the material heater 12 and the medicament heater 20 can be in the forms of an electric heater, an electromagnetic induction heater, a natural gas stove heater and a diesel oil heater.
The material mixer 13 may be in the form of a venturi mixer, a T-type mixer, a flute tube mixer, or the like.
The oxidant proportioning meter 5, the two main paths of the chemical proportioner 21 and the distributed branches are all provided with precise flow meters.
The pressure reducing device 16 includes a capillary pressure reducer, a back pressure valve, a pressure regulating valve, and a multi-stage valve step-by-step pressure reducing device.
The product separator 17 may include a gas-liquid separator and a gas-liquid-solid three-phase separator, depending on the specific nature of the feed.
The agent in the agent storage tank 18 includes alcohols such as methanol, ethanol, ethylene glycol, isopropanol and the like, and nitrates such as sodium nitrate, sodium nitrite, potassium nitrate, lithium nitrate and the like.
The inner wall surface of the supercritical water oxidation reactor 14 is provided with a replaceable lining, such as a titanium lining, a nickel lining and the like, the outer side of the lining is provided with an oxidant spiral channel, the outer side of the oxidant spiral channel is provided with a cooling water spiral channel, and the spiral channel comprises a single spiral channel and a double spiral channel.
The inside of the supercritical water oxidation reactor 14 is provided with a detachable packed bed catalyst, and the upper part of the packed bed catalyst is provided with a flow equalizing plate.
Be equipped with adiabatic heat preservation passageway between supercritical water oxidation reactor 14's material passageway and the oxidant passageway, thermal insulation material such as aerogel felt is filled in the adiabatic passageway, and spiral atomizing nozzle is installed to the material passageway export, and oxidant passageway export and medicament passageway export are equipped with the internal thread and play and revolve the device.
The side of the supercritical water oxidation reactor 14 is respectively provided with 4 segmented oxygen inlet channels and segmented chemical inlet channels, and outlets of contact positions of the segmented oxygen inlet channels and the segmented chemical inlet channels and the inner wall surface lining are provided with a plurality of downward inclined annular holes.
The outer side of the upper part of the supercritical water oxidation reactor 14 is provided with a heater, which comprises an electric heater and an electromagnetic induction heater.
The other side of the supercritical water oxidation reactor 14 is provided with 5 thermocouple temperature measuring points, the first temperature measuring point is positioned on the reaction initial plane, the rest temperature measuring points are respectively positioned behind the segmented oxygen injection positions, and the position of the end cover of the reactor is provided with a pressure measuring point.
The above further optimizations may be used in free combination.
According to the above structure, the present invention provides several embodiments of the corresponding process, and the components such as the valve on which the embodiments are based can refer to fig. 1.
Example 1:
this example takes supercritical water oxidation technology to treat typical nitrogenous organic pyridine as an example, and describes a multifunctional supercritical water enhanced oxidation system in detail:
1) adding proper tap water into a material preparation tank for preparing a reactant pyridine to be treated according to required concentration, starting a stirrer to stir the reactant pyridine uniformly, pressurizing the reactant pyridine to about 25MPa by a material high-pressure pump, preheating the high-pressure material in a first stage by entering an outer tube of a preheater, preheating the material in a second stage (about 400 ℃) by a material heater again because the temperature of the material in the supercritical water oxidation reactor is not enough to preheat the material to required reaction temperature in the initial reaction stage, and entering a material channel at an end cover of the supercritical water oxidation reactor after preheating and boosting the material by the material heater, and entering the inside of the supercritical water oxidation reactor after atomization of a spiral atomization nozzle.
2) The low-temperature liquid oxygen is pressurized to about 25MPa by a high-pressure liquid oxygen pump, then enters a liquid oxygen gasifier for gasification, and the gasified oxygen (about 20 ℃) is stored in an oxygen buffer tank. When two-stage oxygen feeding is adopted, a first oxygen feeding inlet is positioned in an oxidant passage at the end cover of the reactor, and a second oxygen feeding inlet is positioned in an oxidant passage a1 on the side surface of the reactor, an oxidant proportion distribution meter is arranged in advance according to the proportion of the feeding amount of the two-stage oxidant, wherein the feeding amount of the oxidant at the first oxygen feeding inlet is 75% of the total oxidant amount, the feeding amount of the oxidant at the second oxygen feeding inlet is 25% of the total oxidant amount, valves V103 and V104, and valves V110 and Z101 on other oxidant branch passages are opened, and the valves on the other oxidant branch passages are in a closed state. At the moment, the oxidant of the first oxygen injection point on the end cover of the reactor enters the oxidant annular chamber, then enters the reactor through the rotating action of the internal thread to perform homogeneous SCWO reaction with the atomized material on the initial reaction plane, and the oxidant of the second oxygen injection point a1 on the side surface of the reactor passes through the oxidant channel and then is uniformly sprayed out of the annular hole on the inner bushing onto the reaction plane, so that the oxidation reaction of the material and the oxidant is enhanced.
3) When the sectional oxidation coupling wall surface catalysis and the packed bed catalyst are adopted, the lining of the inner wall surface of the reactor is replaced by a titanium lining or a nickel lining with the catalysis function, and MnO is filled in the packed bed catalyst2、Al2O3Heterogeneous gold such as CuOThe material and oxidant pass through flow equalizing plate successively in reactor to produce supercritical water oxidation reaction with catalyst packed bed.
4) When alcohol auxiliary agents such as methanol, ethanol, ethylene glycol, isopropanol and the like are added for assisting co-oxidation, proper tap water is added into a medicament preparation tank for preparation according to the concentration of the required alcohol auxiliary agents, the alcohol auxiliary agents are stirred uniformly by a stirrer, then the alcohol auxiliary agents are pressurized to about 25MPa by a medicament high-pressure pump, and whether a medicament heater is used for properly preheating the alcohol auxiliary agents is determined according to the required process conditions. When only one-time co-oxidation is adopted, the valve V107 is opened, the valve V105 is closed, the alcohol auxiliary agent directly enters the medicament channel on the end cover of the reactor, enters the reactor after being spirally wound by the inner screw, is mixed with the atomized material and the oxidant on the initial reaction plane and generates co-oxidation reaction.
5) The high-temperature high-pressure reaction product after supercritical water enhanced oxidation firstly enters an inner tube of a preheater to preheat a normal-temperature reaction material in a first stage, the residual heat further enters an inner tube of a steam generator to preheat tap water pressurized by a water pump from a water storage tank and enable the tap water to generate corresponding steam capable of being applied industrially, meanwhile, the reaction product is further cooled in the inner tube of the steam generator, the cooled high-pressure product enters a pressure reduction device and is reduced to a proper pressure, and then the high-temperature high-pressure product enters a product separator to separate a gas-liquid two-phase product, wherein the gas-phase product can be directly discharged into the atmosphere, and the liquid-phase product can be used for preparing pure water or industrial reuse water.
Example 2:
the difference from the embodiment 1 lies in the step 1), when the material solution to be treated contains inorganic salt ions, the material is added with proper tap water in a material preparation tank according to the required concentration for blending and stirring uniformly, then the material is pressurized to about 25MPa through a material high-pressure pump, then the high-pressure cold material directly enters a material channel at the end cover of the supercritical water oxidation reactor and is sprayed onto an initial reaction plane through the atomization effect of a spiral atomization nozzle, and simultaneously, a heater on the upper part of the supercritical water oxidation reactor is started to directly heat the material in the reactor to the reaction temperature.
In the step 4), according to the concentration of the required alcohol fuel (methanol, ethanol, ethylene glycol and isopropanol), adding proper tap water into a medicament preparation tank for preparation and uniform stirring, pressurizing the mixture to about 25MPa by a medicament high-pressure pump, heating an alcohol auxiliary agent by a medicament heater, opening a valve V107, closing a valve V105, directly entering the alcohol auxiliary agent into a medicament channel on an end cover of the reactor, entering the reactor after being spirally started by an inner screw, mixing the alcohol auxiliary agent with the preheated material and the oxidant on an initial reaction plane, and carrying out supercritical hydrothermal combustion reaction.
In the step 5), tap water pressurized by a water pump in a water storage tank is divided into two paths, one path of tap water enters a steam generator to be cooled and reacted to obtain a high-temperature and high-pressure product and generate corresponding steam which can be industrially applied, the other path of tap water enters a cooling water inlet g1 of a supercritical water oxidation reactor, the wall surface of the high-temperature reactor which generates hydrothermal combustion reaction is cooled through an upward spiral channel, the safety of the reactor under the hydrothermal combustion condition is ensured, and then the product flows out from a cooling water outlet g2 of an end cover of the reactor. The rest of the procedure was the same as in example 1.
Example 3:
the difference from the embodiment 1 is that in the step 2), the valve V101 is closed, the valve V102 is opened, after the hydrogen peroxide in the hydrogen peroxide storage tank is pressurized to about 25MPa by the high-pressure pump, according to the requirements of the process conditions, it is determined whether the hydrogen peroxide needs to be preheated by using the hydrogen peroxide heater, and then it is determined whether the staged oxygen injection is needed to enter the reactor, and the rest steps are the same as the step of the embodiment 1.
Example 4:
the difference from the embodiment 1 is that in the step 2), the position of the first oxygen injection point is changed, the valve V104 is closed, the valve V103 is opened, the pressurized oxidant (oxygen or hydrogen peroxide) enters the inlet e of the spiral oxidant channel at the bottom of the supercritical water oxidation reactor, the oxidant is preheated in the spiral channel by the high-temperature reaction fluid in the supercritical water oxidation reactor, and is uniformly sprayed out to the initial reaction plane at the oxidant injection point f at the upper part of the reactor through the annular hole on the inner bushing to perform SCWO reaction with the atomized material, and the rest steps are the same as the steps in the embodiment 1.
Example 5:
the difference from the example 1 lies in that in the step 2), the position of the secondary oxidant injection point and the number of the oxidant injection points can be adjusted by adjusting the on-off of the valves on different branch channels of the oxidant on the side surface of the reactor, and the rest steps are the same as the step of the example 1.
Example 6:
the difference from example 1 is that in step 3), the lining of the inner wall surface of the reactor can be replaced by an inert lining having no catalytic action, such as an aluminum lining, the packed bed catalyst inside the reactor can be removed, and the rest of the steps are the same as those of example 1.
Example 7:
the difference from the embodiment 1 is that in the step 4), when only one-time co-oxidation is adopted, the valve V107 is closed, the valve V105 is opened, the alcohol auxiliary agent enters the mixer to be uniformly mixed with the preheated material, then enters the material channel at the end cover of the reactor together, enters the reactor together to perform co-oxidation reaction with the oxidant after the atomization action of the spiral atomization nozzle, and the rest steps are the same as the step of the embodiment 1.
Example 8:
the difference from the embodiment 1 lies in that in the step 4), the side surface of the reactor is also provided with different sectional injection channels of the medicament, the valve V105 is closed, the valve V107 is opened, the alcohol injection amount of the primary alcohol injection point and the secondary alcohol injection point is preset through a medicament proportion meter, the secondary injection position of the alcohol auxiliary agent and the number of the sectional alcohol injection points can be flexibly adjusted through controlling the opening and closing of the valves on different medicament branch channels, and the rest steps are the same as the step of the embodiment 1.
Example 9:
the difference from the embodiment 1 is that in the step 4), the alcohol auxiliary agents such as methanol, ethanol, ethylene glycol, isopropanol and the like are replaced by (nitrite) salts such as sodium nitrate, sodium nitrite, potassium nitrate, lithium nitrate and the like, wherein the nitrite is prepared and uniformly stirred with tap water in a medicament preparation tank according to the required concentration, and then is pressurized to about 25MPa by a medicament high-pressure pump, and then directly enters a medicament channel on an end cover of the reactor and enters the reactor after being spirally wound by an inner screw; or directly enters the mixer to be uniformly mixed with the material, then enters the material channel at the end cover of the reactor together, enters the reactor together after the atomization of the spiral atomization nozzle to perform strong oxidation reaction with the oxidant, and the rest steps are the same as the steps in the embodiment 1.
Example 10:
the difference from the example 1 is that in the step 5), when the refractory organic pollutants containing solid particles are treated, the cooled and depressurized product enters a gas-liquid-solid three-phase separator, the separated gas-phase product is directly discharged into the atmosphere, the liquid-phase product can be used for preparing pure water or industrial reuse water, the stable solid-phase product can be recycled for making bricks and preparing ceramic particles, and the rest steps are the same as the step in the example 1.
In conclusion, the invention couples various intensified oxidation technologies such as reactor inner wall surface catalysis, heterogeneous metal oxide catalysis, auxiliary agent co-oxidation, sectional co-oxidation and inorganic salt catalytic oxidation and the like in a supercritical water oxidation system at one time, wherein the combination of one or more intensified technologies can realize the synergistic and efficient removal of nitrogen-containing organic pollutants COD and ammonia nitrogen under relatively mild reaction conditions, thereby reducing the system operation conditions and the equipment investment cost and improving the economy and the safety reliability of the system. Meanwhile, the specially designed supercritical water oxidation reactor used in the invention can not only strengthen the uniform mixing of the reaction materials, the oxidant and the medicament on different reaction planes and improve the chemical reaction rate, but also realize the incidence of cold materials aiming at the saline materials, thereby avoiding the salt crystallization, deposition and blockage of the preheater, the heater and other equipment and connecting pipelines thereof in the preheating process and improving the reliability of the system operation.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification, equivalent replacement, improvement, etc. made on the basis of the technical idea proposed by the present invention are within the protection scope of the claims of the present invention.
Claims (10)
1. A multi-functional type supercritical water intensification oxidation system for refractory nitrogenous and high-salinity organic pollutants, which is characterized by comprising:
a supercritical water oxidation unit comprising a supercritical water oxidation reactor (14);
the system comprises an oxidant pretreatment unit and a hydrogen peroxide treatment unit, wherein the oxidant pretreatment unit is divided into two paths, one path comprises a liquid oxygen storage tank (1), a high-pressure liquid oxygen pump (2), a liquid oxygen gasifier (3) and an oxygen buffer tank (4) which are sequentially communicated, the other path comprises a hydrogen peroxide storage tank (6), a hydrogen peroxide high-pressure pump (7) and a hydrogen peroxide heater (8) which are sequentially communicated, an outlet of the hydrogen peroxide heater (8) is connected with an outlet of the oxygen buffer tank (4), the two paths are divided into two paths through an oxidant proportion distributor (5) after being connected, one path is directly connected with an oxidant inlet of an end cover of a supercritical water oxidation reactor (14), and the other path is connected with each segmented oxygen inlet on the side surface of the supercritical water oxidation reactor;
the material pretreatment unit comprises a material preparation tank (9), a material high-pressure pump (10), a preheater (11), a material heater (12) and a material mixer (13) which are sequentially communicated, wherein the outer pipe of the preheater (11) is positioned on a communicating pipeline, and the outlet of the material mixer (13) is connected with the material inlet of a supercritical water oxidation reactor (14);
the reagent pretreatment unit comprises a reagent preparation tank (18), a reagent high-pressure pump (19) and a reagent heater (20) which are sequentially communicated, wherein the outlet of the reagent heater (20) is divided into two paths, one path is connected with the inlet of the material mixer (13), the other path is divided into two paths through a reagent proportion distribution meter (21), one path is directly connected with the reagent inlet of the end cover of the supercritical water oxidation reactor (14), and the other path is connected to each sectional reagent inlet on the side surface of the supercritical water oxidation reactor (14);
the product subsequent treatment unit comprises a steam generator (15), a pressure reduction device (16) and a product separator (17) which are sequentially communicated, wherein the outlet of the supercritical water oxidation reactor (14) is connected with the inlet of the inner tube of the material preheater (11), the outlet of the inner tube of the material preheater (11) is connected with the inlet of the outer tube of the steam generator (15), the outlet of the outer tube of the steam generator (15) is connected with the inlet of the pressure reduction device (16), and the outlet of the pressure reduction device (16) is connected with the inlet of the product separator (17);
the water supply unit comprises a water storage tank (22), a water pump (23) and a steam storage tank (24) which are sequentially communicated, wherein the outlet of the water pump (23) is divided into two paths, one path of outlet is connected with the inlet of an inner tube of a steam generator (15), the outlet of the inner tube of the steam generator (15) is connected with the inlet of the steam storage tank (24), and the other path of outlet is directly connected with a cooling water inlet of a supercritical water oxidation reactor (14).
2. The system of claim 1, wherein the hydrogen peroxide storage tank (6) comprises a light-shielding and cold-keeping device, the material blending tank (9) and the chemical blending tank (18) are provided with stirrers, the stirrers are frame stirrers, paddle stirrers, turbine stirrers or ribbon stirrers, the preheater (11) and the steam generator (15) are tube-in-tube heat exchangers or shell-and-tube heat exchangers, the hydrogen peroxide heater (8), the material heater (12) and the chemical heater (20) are electric heaters, electromagnetic induction heaters, natural gas furnace heaters or diesel heaters, the material mixer (13) is a Venturi mixer, a T-type mixer or a flute-type mixer, and the pressure reduction device (16) is a capillary pressure reducer, The device comprises a back pressure valve, a pressure regulating valve or a multi-stage valve step-by-step pressure reduction device, a product separator (17) is a gas-liquid separator or a gas-liquid-solid three-phase separator, a heater is arranged on the outer side of the upper part of a supercritical water oxidation reactor (14), and the heater is an electric heater or an electromagnetic induction heater.
3. The multi-functional supercritical water enhanced oxidation system for nitrogen and high-salt organic pollutants difficult to degrade according to claim 1 is characterized in that precise flow meters are installed on the oxidant proportion distribution meter (5), the two main paths of the chemical agent proportion regulator (21) and the distributed branch paths.
4. The multifunctional supercritical water enhanced oxidation system for refractory nitrogen and high-salinity organic pollutants according to claim 1, characterized in that the agent in the agent storage tank (18) is one or more of alcohols, nitrates or nitrites.
5. The system of claim 4, wherein the alcohol is methanol, ethanol, ethylene glycol or isopropanol, the nitrate is sodium nitrate, potassium nitrate or lithium nitrate, and the nitrite is sodium nitrite.
6. The multifunctional supercritical water enhanced oxidation system for refractory nitrogen-containing and high-salt organic pollutants as claimed in claim 1, wherein the inner wall of the supercritical water oxidation reactor (14) is provided with a replaceable liner made of titanium or nickel, an oxidant spiral channel is arranged on the outer side of the liner, a cooling water spiral channel is arranged on the outer side of the oxidant spiral channel, and the spiral channel is a single spiral channel or a double spiral channel.
7. The system of claim 1, wherein the supercritical water oxidation reactor (14) is provided with a removable packed bed catalyst, and the packed bed catalyst is provided with a flow equalizing plate on the top.
8. The system of claim 1, wherein a heat insulation and preservation channel is arranged between the material channel and the oxidant channel of the supercritical water oxidation reactor (14), the heat insulation channel is filled with heat insulation materials, the material channel outlet is provided with a spiral atomizing nozzle, and the oxidant channel outlet and the chemical channel outlet are provided with internal thread screwing devices.
9. The system of claim 1, wherein the side of the supercritical water oxidation reactor (14) is provided with 4 segmented oxygen inlet channels and segmented chemical inlet channels from top to bottom, and a plurality of downward inclined annular holes are arranged at the outlets of the contact positions of the segmented oxygen inlet channels and the segmented chemical inlet channels with the inner wall surface lining.
10. The system of claim 9, wherein 5 thermocouple temperature measurement points are arranged on the upper and lower sides of the supercritical water oxidation reactor (14), the first temperature measurement point is located on the reaction initiation plane, the other temperature measurement points are respectively located behind the segmented oxygen inlet position, and a pressure measurement point is arranged at the end cover position of the reactor.
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| CN111632569A (en) * | 2020-05-24 | 2020-09-08 | 西安交通大学 | Flow corrosion-salt deposition device for supercritical water oxidation reaction coupling |
| CN112408575A (en) * | 2020-10-22 | 2021-02-26 | 西安交通大学 | Nitrogen removal device for supercritical water oxidation of high-concentration nitrogen-containing organic wastewater |
| CN112811567A (en) * | 2021-01-20 | 2021-05-18 | 贵州航天朝阳科技有限责任公司 | Supercritical water oxidation reaction device and control method |
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| CN114835237A (en) * | 2022-04-29 | 2022-08-02 | 西安交通大学 | Supercritical water oxidation treatment system for organic waste and regulation and control method thereof |
| CN114790029B (en) * | 2022-04-29 | 2024-02-06 | 西安交通大学 | Pollutant harmless regulation and control system and method based on supercritical water oxidation technology |
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