CN109851131A - Supercritical water oxidation apparatus and method for processing organic wastewater - Google Patents
Supercritical water oxidation apparatus and method for processing organic wastewater Download PDFInfo
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- CN109851131A CN109851131A CN201910108899.1A CN201910108899A CN109851131A CN 109851131 A CN109851131 A CN 109851131A CN 201910108899 A CN201910108899 A CN 201910108899A CN 109851131 A CN109851131 A CN 109851131A
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Abstract
Present disclose provides a kind of supercritical water oxidation apparatus, including reactor, the reactor includes reactor shell, heating device and blender.Wherein, oxidant feed mouth, organic matter feed inlet and discharge port are provided in reactor shell.Heating device is used to promote the temperature in the reactor enclosure body.Blender, including shaft, the shaft pass through the reactor shell.The disclosure additionally provides a kind of method for processing organic wastewater.
Description
Technical field
This disclosure relates to supercritical water oxidation apparatus and method for processing organic wastewater.
Background technique
Supercritical water oxidation method is a kind of novel wet oxidation technology.By being faced using debirs, water, oxygen super
In boundary's aqueous systems the characteristics of complete miscibility, oxidation operation is decomposed into carbon dioxide, water and inorganic salts etc., to complete to having
The processing of machine waste liquid.Generally, supercritical water refer to temperature be more than 374 DEG C, pressure be more than 22Mpa a kind of special state
Water.Debirs and the oxygen complete miscibility in supercritical water system under supercritical water state, when supercritical water temperature is more than
550 DEG C, inorganic salts are zero in solubility wherein.Using this performance of supercritical water, dioxy can be converted by organic matter
Change carbon, water and inorganic salts.
Currently, research is thought, supercritical water oxidation method decomposition efficiency is high, process cycle is short, the flames of anger, secondary waste are few,
It is environmental-friendly, it is suitble to a variety of debirs of processing, can be applied to environmental protection, chemical industry, coal gasification, nuclear power and thermoelectricity, new material closes
It is a kind of processing technique of great potential at waiting in numerous areas.
But inventor has found in the implementation of the present invention, in the related art, at overcritical water oxidization reactor
When managing radioactive liquid waste, it is easy to appear crystalline growth in the reactor comprising inorganic salts in reaction product, and then deposits, bonding,
Blocking pipeline.
Summary of the invention
An aspect of this disclosure provides a kind of supercritical water oxidation apparatus, including reactor, and the reactor includes
Reactor shell, heating device and blender.Wherein, oxidant feed mouth, organic matter charging are provided in reactor shell
Mouth and discharge port.Heating device is used to promote the temperature in the reactor enclosure body.Blender, including shaft, the shaft
Across the reactor shell.
According to the embodiment of the present disclosure, the shaft passes through the discharge port.
According to the embodiment of the present disclosure, the stirrer configuration has ammeter and/or voltmeter.
According to the embodiment of the present disclosure, the reactor further includes cooling device, and the cooling device includes being arranged described
At least one set of coolant jacket outside reactor shell, wherein the heating device includes being arranged outside the reactor shell
At least one set of heating mantle, the reactor shell includes close to the first area of the oxidant feed mouth and close to described
The second area of discharge port, the heating device are set to the outside of the first area, and the cooling device is set to described
The outside of second area.
According to the embodiment of the present disclosure, the reactor shell includes the first end wall, side wall and opposite with the first end wall
Second end wall, the oxidant feed mouth are set to first end wall, and the organic matter feed inlet is set to the side wall, institute
It states discharge port and is set to second end wall.
According to the embodiment of the present disclosure, the reactor further includes liner, is set to second end wall, and to described first
The direction of end wall extends, and the discharge port is set to the inside of the liner, wherein the organic matter feed inlet and described first
The distance of end wall is greater than the organic matter feed inlet at a distance from second end wall.
According to the embodiment of the present disclosure, the interior laying-in aluminising, shot-peening hammering and spraying thermal barrier coating processing, the thermal boundary
Coating includes the multiple aluminium layers and multiple alumina layers being arranged alternately.
According to the embodiment of the present disclosure, the supercritical water oxidation apparatus further includes from separation outer barrel, the separation outer barrel certainly
It is inside provided with evaporation tank, condensation reservoir and condenser pipe, the reactor is set to described from the inside for separating outer barrel.
According to the embodiment of the present disclosure, the evaporation tank is connected with the discharge port, in the evaporation tank and the discharging
Counterbalance valve is equipped between mouthful.
According to the embodiment of the present disclosure, the condensation reservoir is set to the top of the evaporation tank, and the condenser pipe is set to institute
The top of condensation reservoir is stated, so that the gas evaporated in the evaporation tank in liquefied situation, liquefies at the condenser pipe
To liquid can fall after rise into the condensation reservoir.
According to the embodiment of the present disclosure, cooling tube is provided in the evaporation tank.
According to the embodiment of the present disclosure, slag-drip opening is provided in the evaporation tank.
According to the embodiment of the present disclosure, discharge outlet is provided in the condensation reservoir.
It is described to be provided with exhaust outlet from the top of separation outer barrel according to the embodiment of the present disclosure.
Described that cooling interior bucket is provided with from separation outer barrel according to the embodiment of the present disclosure, the condenser pipe is set to described
The inside of cooling interior bucket, the condensation reservoir are formed in the bottom of the cooling interior bucket, are provided on the bucket wall of the cooling interior bucket
Multiple ducts.
According to the embodiment of the present disclosure, the evaporation tank is connected to by reactor outlet pipe with the reactor, the evaporation
Casing is provided in pond, the reactor outlet pipe accesses in described sleeve pipe, and described sleeve pipe is equipped with aperture.
According to the embodiment of the present disclosure, temperature sensor is provided in the evaporation tank, in condensation reservoir, in reactor shell.
According to the embodiment of the present disclosure, pressure sensor is provided in the reactor enclosure body.
According to the embodiment of the present disclosure, the slag-drip opening is provided with pH on-line monitoring meter.
According to the embodiment of the present disclosure, the exhaust ports are provided with volatile organic matter on-line monitoring device.
According to the embodiment of the present disclosure, the discharge outlet is provided with COD on-line monitoring device.
Another aspect of the disclosure provides a kind of method for processing organic wastewater, passes through overcritical water oxygen described above
Processing organic wastewater is set in makeup, and the discharge outlet of the overcritical water oxidization reactor is provided with counterbalance valve, the method includes
The reactor is heated, when the temperature in the reactor enclosure body reaches the first temperature, starts the blender, and by the
One solution is inputted in the reactor enclosure body by the organic matter feed inlet, and oxidant is defeated by the oxidant feed mouth
Enter in the reactor enclosure body, until the temperature in the reactor enclosure body reaches second temperature, wherein the second temperature is not
Less than 600 DEG C, when the pressure in the reactor enclosure body reaches predetermined pressure, the counterbalance valve is opened, by the organic waste
Water is inputted in the reactor enclosure body by the organic matter feed inlet, wherein the organic wastewater is under supercritical water environment
It is oxidized, and is discharged from the discharge port.
According to the embodiment of the present disclosure, the second temperature is between 650 DEG C to 800 DEG C.
According to the embodiment of the present disclosure, first solution includes sucrose solution.
According to the embodiment of the present disclosure, the oxidant includes oxygen.
According to the embodiment of the present disclosure, the stirrer configuration has ammeter and voltmeter, is respectively used to detect the stirring
The electric current and voltage of device, the method also includes reducing institute when the electric current and/or voltage of the blender reach predetermined value
State the feed rate of at least one of oxidant feed mouth and organic matter feed inlet.
According to the embodiment of the present disclosure, the overcritical water oxidization reactor further includes cooling device, the reactor shell
The second area of first area and the close discharge port including the close oxidant feed mouth, the method also includes
The heating device and the cooling device are controlled, controls the temperature of the first area within a predetermined range, and control
The temperature for making the second area makes the temperature of the effluent of the discharge port be not less than 120 DEG C.
According to the embodiment of the present disclosure, the temperature of the effluent of the discharge port is between 150 DEG C to 300 DEG C.
According to the embodiment of the present disclosure, the supercritical water oxidation apparatus further includes from separation outer barrel, the separation outer barrel certainly
It is inside provided with evaporation tank, condensation reservoir and condenser pipe, the reactor is set to described from the inside for separating outer barrel, wherein described
Evaporation tank is connected with the discharge port, and counterbalance valve, the condensation reservoir setting are equipped between the evaporation tank and the discharge port
In the top of the evaporation tank, the condenser pipe is set to the top of the condensation reservoir, the gas evaporated in the evaporation tank
At the condenser pipe in liquefied situation, liquid can be fallen after rise into the condensation reservoir, and the supercritical water oxidation apparatus is also
Including monitoring system, the method also includes in response to user's input or in response to the monitoring result of the monitoring system, control
Following at least one: the pressure and/or flow of oxide feed；The pressure and/or flow of organic matter feed；The reactor
And/or the temperature of the evaporation tank；And/or the state of the counterbalance valve.
The supercritical water oxidation system and method for the disclosure can be by the disturbances of blender, the nothing that effectively prevent in product
There is crystalline growth in the reactor in machine salt, and then deposits, bonding, and blocking pipeline improves service life of equipment.
Detailed description of the invention
In order to which the disclosure and its advantage is more fully understood, referring now to being described below in conjunction with attached drawing, in which:
Fig. 1 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus according to the embodiment of the present disclosure；
Fig. 2 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus according to another embodiment of the disclosure；
Fig. 3 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus according to another embodiment of the disclosure:
Fig. 4 diagrammatically illustrates the schematic diagram of the casing according to the embodiment of the present disclosure；
Fig. 5 diagrammatically illustrates the schematic diagram of the cooling interior bucket according to the embodiment of the present disclosure；And
Fig. 6 diagrammatically illustrates the flow chart of the method for processing organic wastewater according to the embodiment of the present disclosure.
Specific embodiment
Hereinafter, will be described with reference to the accompanying drawings embodiment of the disclosure.However, it should be understood that these descriptions are only exemplary
, and it is not intended to limit the scope of the present disclosure.In the following detailed description, to elaborate many specific thin convenient for explaining
Section is to provide the comprehensive understanding to the embodiment of the present disclosure.It may be evident, however, that one or more embodiments are not having these specific thin
It can also be carried out in the case where section.In addition, in the following description, descriptions of well-known structures and technologies are omitted, to avoid
Unnecessarily obscure the concept of the disclosure.
Term as used herein is not intended to limit the disclosure just for the sake of description specific embodiment.It uses herein
The terms "include", "comprise" etc. show the presence of the feature, step, operation and/or component, but it is not excluded that in the presence of
Or add other one or more features, step, operation or component.
There are all terms (including technical and scientific term) as used herein those skilled in the art to be generally understood
Meaning, unless otherwise defined.It should be noted that term used herein should be interpreted that with consistent with the context of this specification
Meaning, without that should be explained with idealization or excessively mechanical mode.
It, in general should be according to this using statement as " at least one in A, B and C etc. " is similar to
Field technical staff is generally understood the meaning of the statement to make an explanation (for example, " system at least one in A, B and C "
Should include but is not limited to individually with A, individually with B, individually with C, with A and B, with A and C, have B and C, and/or
System etc. with A, B, C).Using statement as " at least one in A, B or C etc. " is similar to, generally come
Saying be generally understood the meaning of the statement according to those skilled in the art to make an explanation (for example, " having in A, B or C at least
One system " should include but is not limited to individually with A, individually with B, individually with C, with A and B, have A and C, have
B and C, and/or the system with A, B, C etc.).
In accordance with an embodiment of the present disclosure, in order to realize nuclear power station and other nuclear facilities radioactive liquid waste volume reduction harm reduction,
Present disclose provides a kind of supercritical water oxidation apparatus and method, the supercritical water oxidation apparatus provided by the disclosure and side
Method can convert inorganic matter by supercritical water oxidation for organic wastewater, using reaction residual temperature spontaneous evaporation, will put in organic matter
The recycling of penetrating property metallic element, realizes the purpose of waste minimum.Among practical application, the supercritical water of the embodiment of the present disclosure
Oxidative system and method processing Radioactive myocardial damage processing capacity reach 1-10kg/h, and volume reduction ratio reaches 30-100 times, outflow
Object is distilled water reusable, and purification gas can be with direct emission.
Fig. 1 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus according to the embodiment of the present disclosure.
As shown in Figure 1, the supercritical water oxidation apparatus includes reactor 100, the reactor 100 includes reactor shell
110, heating device 120 and blender 130.Wherein, oxidant feed mouth 111, organic matter are provided in reactor shell 110
Feed inlet 112 and discharge port 113.Heating device 120 is used to promote the temperature in the reactor shell 110.Blender
130, including shaft, the shaft is across the reactor shell.
The embodiment of the present disclosure to the shape, material, size of reactor shell 110 without limitation.For example, reactor enclosure
Body 110 can be cylindrical type, and material can be as INCONEL625, and 110 internal diameter of reactor shell can be 80~219mm, example
Such as can be 168mm, thickness for example may be about 25mm, length can be 1000~6000mm, such as can be 3000mm.
According to the embodiment of the present disclosure, heating device 120 is used to improve the temperature of reactor shell 110, and then to reactor
The chamber heating formed in shell 110.The embodiment of the present disclosure to the type of heating device 120 without limitation.For example, heating device
120 can be one or more groups of heating mantles, and heating mantle can be set in the outside of reactor shell 110 by the embodiment of the present disclosure,
To transmitting heat inside reactor shell 110 by way of heat transfer.
Fig. 2 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus 200 according to another embodiment of the disclosure.Fig. 2
Reactor shell 210, heating device 220 and the blender 230 illustrated can refer to reactor shell illustrated in Figure 1
110, heating device 120 and blender 130.
According to the embodiment of the present disclosure, blender 230 for example may include shaft 231, and shaft 231 passes through reactor shell
210.The reactor 200 can tilt installation, gradient 10%, and discharge port 213 is in lowermost end, which uses
It is stirred in the substance in reactor 200.Supercritical water reaction product is generally superfine particulate matter, not crystalline growth
Condition, as long as there is disturbance, particulate matter will not be deposited, be bonded, and ultra-fine inorganic salt is effectively prevent to form crystal blocking discharge port 213.
For example, blender 230 may include interior magnet rotor 232 and outer magnet rotor 233, in the case where energization, in outer magnet rotor 233
Under drive, interior magnet rotor 232 drives shaft 231 and stirrer rotation.The blender 230 can for example keep the revolving speed of 800rpm
It is stirred, so that supercritical water reaction product grain keeps suspending without depositing.
According to the embodiment of the present disclosure, shaft 231 passes through the discharge port 213.As shown in Fig. 2, the discharge port 213 is L-type,
Shaft 231 passes through reactor shell 210 and protrudes into reactor shell 210 partially across the discharge port 213, is discharging
Mouth 213 nearby stirs, and prevents blocking discharge port 213.
According to the embodiment of the present disclosure, the blender 230 is configured with ammeter and/or voltmeter, for monitoring blender
Electric current and voltage, the pressure when the electric current of blender 230 and voltage increase and reaches predetermined value, inside reactor 200
It is larger, need to reduce the feed rate of two feed inlets 211 and 212, or even pause charging.
According to the embodiment of the present disclosure, the reactor 200 further includes cooling device 240, is used for after the start of the reaction, to anti-
It answers device 200 to cool down, prevents the temperature of reactor 200 excessively high, shorten service life of equipment and even cause danger.The cooling
Device 240 for example may include at least one set of coolant jacket being arranged in outside the reactor shell 210.Coolant jacket may include
Two parts can be fixed between two parts by fixation hole and bolt, cooling water can be filled in each part.The disclosure
The cooling device of embodiment may include one or more groups of coolant jackets, can be by adjusting use state in equipment operation
The quantity of coolant jacket realizes the control to the temperature of reactor.Similarly, the heating device of the embodiment of the present disclosure may include one
Group or multiple groups heating mantle can be realized by adjusting the quantity of the heating mantle of use state to reactor in equipment operation
The control of temperature.
According to the embodiment of the present disclosure, the reactor shell 210 includes close to the firstth area of the oxidant feed mouth 211
The second area 20 of domain 10 and the close discharge port 213, the heating device 220 are set to the outer of the first area 10
Portion, the cooling device 240 are set to the outside of the second area 20.According to the embodiment of the present disclosure, supercritical water oxidation exists
It is completed in first area 10, during product is flowed through second area 20 to discharge port 213, the device 240 that is cooled is cooling, arrives
Temperature when up to discharge port is about 150~300 DEG C.
As shown in Fig. 2, according to the embodiment of the present disclosure, reactor shell 210 include the first end wall 214, side wall 215 and with
The second opposite end wall 216 of first end wall 214, oxidant feed mouth 211 are set to first end wall 214, organic matter charging
Mouth 212 is set to the side wall 215, and discharge port 213 is set to the second end wall 216.Optionally, discharge port 213 also can be set
On side wall 215.
According to the embodiment of the present disclosure, reactor 200 further includes liner 250, is set to second end wall 216, and to institute
The direction for stating the first end wall 214 extends, and the discharge port 213 is set to the inside of the liner 250, wherein the organic matter
Feed inlet 212 be greater than at a distance from first end wall 214 the organic matter feed inlet 212 and second end wall 216 away from
From.That is, organic matter feed inlet 212 is closer to the second end wall 216, after organic matter enters reactor 200, along the outside of liner 250
It is mobile to the direction of the first end wall 214, until reaching near oxidant feed mouth 211, with oxidant under supercritical water environment
Oxidation reaction occurs.The design enables organic matter to be preheated between liner and shell, and makes the temperature of liner
It is unlikely to excessively high, prolongs the service life.
According to the embodiment of the present disclosure, the material of the liner 250 for example can be high-temperature alloy material GH4169, and internal diameter can
To be 40-133mm, such as it can be 108mm, length can be 1000-6000mm, such as can be 3500mm.
According to the embodiment of the present disclosure, which is included aluminising, shot-peening hammering and spraying thermal barrier coating processing, institute
Stating thermal barrier coating includes the multiple aluminium layers and multiple alumina layers being arranged alternately.It is equivalent to and generates corrosion-inhibiting coating in interior lining,
And under the high temperature action of supercritical water, interior lining forms one layer of fine and close gel layer, prevents supercritical water and inner liner metal
Contact and corrosion.
In accordance with an embodiment of the present disclosure, the key condition for forming fine and close gel layer is that have one between metal and gel layer
The fine and close particulate metal atom of layer.On the one hand, this layer of special metallic atom is connected by metallic bond with base metal.Another party
Face is connected in the form of chemical bond with gel layer again.In order to prepare this layer of metallic atom, embodiment of the disclosure uses Ni-based gold
Belong to, aluminising processing is carried out to metal body first, use shot-peening hammering metal surface later, to form fine and close metal aluminium atom
Layer, sprays thermal barrier coating later, and by metallic aluminium, 6~8 layers of alternating spray of aluminum oxide ceramic layer, metal surface is formed
Thermal barrier coating, thickness about 2~3mm.After thermal barrier coating encounters supercritical water, this layer of thermal barrier coating translates into fine and close gel
Layer.Gel layer can prevent contact and corrosion of the supercritical water with inner liner metal.When 700 DEG C -800 DEG C of reaction center temperature,
Thermal barrier coating surface temperature is maintained at 650 DEG C -750 DEG C, and liner organism temperature is maintained at 550 DEG C -650 DEG C.
According to the embodiment of the present disclosure, reactor 200 can also include at least one temperature sensor, described super for obtaining
The temperature of at least one position of critical oxidation reactor.For example, the both ends and centre of liner 250 can be equipped with temperature spy
Temp probe can be set between heating device 220 and reactor shell 210 in head.
According to the embodiment of the present disclosure, the reactor 200 further includes at least one pressure sensor, described anti-for obtaining
Answer the pressure of at least one position of device.For example, the both ends of reactor 200 can be equipped with pressure gauge, for detecting reactor 200
Internal pressure.
According to the embodiment of the present disclosure, which can be used oxidant feeding device and provides oxidant to it.Oxidation
Agent for example can be liquid oxygen, oxygen, hydrogen peroxide etc., and the embodiment of the present disclosure can be using oxygen as oxidant.According to the disclosure
Embodiment, the oxidation agent feeding device for providing oxygen for example may include oxygen cylinder group, oxygen pressing pump, high-pressure oxygen cylinder
And check valve.
According to the embodiment of the present disclosure, which can be used organic matter feeding device and is fed to it, organic matter
Feeding device for example may include the first water tank, the second water tank, peristaltic pump, high-pressure pump and check valve, wherein the high-pressure pump
It is communicated respectively with the first water tank and peristaltic pump, the peristaltic pump is communicated with second water tank.Wherein, the first water tank can be used for
Organic wastewater is stored, the second water tank can be used for storing sucrose solution.
Fig. 3 diagrammatically illustrates the schematic diagram of the supercritical water oxidation apparatus 300 according to another embodiment of the disclosure.
As shown in figure 3, supercritical water oxidation apparatus 300 on the basis of previous embodiment, further includes from separation outer barrel
320, it is provided with evaporation tank 321, condensation reservoir 322 and condenser pipe 323 from separating in outer barrel 320, the reactor 310 is set to institute
It states from the inside for separating outer barrel 320.The reactor 310, including oxidant feed mouth 311, organic matter feed inlet 312, discharge port
313, agitating device 314, heating device 316, cooling device 315 etc. are referred to the embodiment of Fig. 2 description, no longer superfluous herein
It states.The supercritical water oxidation apparatus is integrated, and number of devices is few, and function is concentrated, and processing capacity is high, since reactor is
Can also play a protective role from separation outer barrel to the external world outside reactor is arranged in high-temperature high-pressure apparatus.
According to the embodiment of the present disclosure, evaporation tank 321 is connected with discharge port 313, in the evaporation tank 321 and the discharging
Counterbalance valve 340 is equipped between mouth 313.
According to the embodiment of the present disclosure, the condensation reservoir 322 is set to the top of the evaporation tank 321, the condenser pipe 323
It is set to the top of the condensation reservoir 322, so that the gas evaporated in the evaporation tank 321 liquid at the condenser pipe 323
In the case where change, the liquid to liquefy can be fallen after rise into the condensation reservoir 322.
According to the embodiment of the present disclosure, after counterbalance valve 340, pressure is gradually recovered as normal pressure, and effluent is also faced by super
Boundary's state reverts to gas-liquid-solid tri-state.Since the effluent of reactor 310 is the temperature of high-temperature, high pressure fluid, such as effluent itself
It is 150~300 DEG C, pressure 25MPa, in order to evaporate high-temperature, high pressure fluid steadily, can be arranged in evaporation tank 321 cold
But pipe 324 allow effluent always in fluidized state.I.e. cooling tube 324 stablizes the temperature of liquid in evaporation tank 321
In target temperature range, for example, it may be allowing liquid to stablize boiling in evaporation tank 321 at 100 DEG C or so.
According to the embodiment of the present disclosure, slag-drip opening 325 is also provided in evaporation tank 321, for being discharged in evaporation tank 321
Non-volatile salt slag.PH on-line monitoring meter can be set in the slag-drip opening 325, in normal conditions, due to generating
Carbon dioxide, the pH value of the effluent of slag-drip opening are about 2 or so, if there is obvious rising, can reduce organic matter feed dress
The temperature or pressure of the feed flow or raising reactor 310 set.
According to the embodiment of the present disclosure, it is provided with discharge outlet 326 in the condensation reservoir 322, for being discharged in condensation reservoir 322
Water.Drainage arrangement may include more radiant tubes and an endless tube, improve drainage efficiency.The water of discharge is distilled water, nuisance
Matter concentration is lower than ten a ten thousandths.COD (COD) on-line monitoring device can be set in discharge outlet 326, water quality is carried out
Monitoring can reduce the feed flow of organic matter feeding device or improve the temperature or pressure of reactor 310 if COD content increases
Power keeps reaction more abundant.
According to the embodiment of the present disclosure, the top from separation outer barrel 320 is provided with exhaust outlet 327, for dioxy to be discharged
Change the purification gas such as carbon.Gas-filtering device can be set at exhaust outlet 327, such as may include active carbon Filter column and height
Filter is imitated, to guarantee that discharge gas meets discharge standard.According to the embodiment of the present disclosure, can also be arranged at exhaust outlet 327
Volatile organic matter (VOC) monitors device on-line, is monitored to gas, if VOC content increases, can reduce organic matter feed
The feed flow of device or the temperature or pressure for improving reactor 310, keep reaction more abundant.
According to the embodiment of the present disclosure, the supercritical water oxidation apparatus 300 further includes water cooler, is used for the condensation
Pipe 323 supplies water, and can also supply water to the cooling device 315 in reactor 310.
In the related art, carbon dioxide, water and inorganic salts are converted for organic matter by overcritical water oxidization reactor
Later, it generally requires through at the multiple equipments such as supercooling equipment, gas-liquid separation equipment, liquid cooling equipment, gas cooling equipment
Reason, could separate carbon dioxide, water and inorganic salts.Not only process flow is long for this processing mode, and equipment is more, and cost
It is high.By embodiment of the disclosure, using the effluent from separation outer barrel processing high temperature (120~300 DEG C), so that salt slag is steaming
Bottom of pond portion to be sent out to be concentrated by evaporation, water evaporates in evaporation tank, and it is cooling by condenser pipe, it can be discharged from the discharge outlet of condensation reservoir, it is clean
Net gas can directly be discharged from the top of separation equipment.The separation equipment of the disclosure can be realized simultaneously the separation of mixture,
Not only process flow is short, but also has reached and equipment one-time investment and equipment operating cost is effectively reduced, and realizes Spent Radioactive
Object volume reduction to the maximum extent.By taking radioactive cesium and strontium as an example, after evaporation tank evaporates, decontamination factor can achieve radioactive cesium
105, less than ten a ten thousandths of caesium concentration in evaporation water, evaporation can achieve the decontamination factor of strontium for caesium in vapor
109, therefore the available deep purifying of steam.
According to the embodiment of the present disclosure, the supercritical water oxidation system further includes monitoring system, and the monitoring system includes
Following at least one described above: it is arranged in the reactor shell, the temperature sensor in evaporation tank, in condensation reservoir；
Pressure sensor in the reactor enclosure body is set；The pH on-line monitoring meter of the slag-drip opening is set；It is arranged described
The volatile organic matter of exhaust ports monitors device on-line；And/or the COD of the discharge outlet is set and is supervised online
Survey device.The supercritical water oxidation system further includes control system, for inputting in response to user or in response to monitoring system
The monitoring result of system controls following at least one: the pressure and/or flow of oxide feed；Organic matter feed pressure and/or
Flow；The temperature of the reactor and/or evaporation tank；And/or the state of the counterbalance valve 340.
Fig. 4 diagrammatically illustrates the schematic diagram of the casing 410 according to the embodiment of the present disclosure.
As shown in figure 4, evaporation tank 400 is by reactor outlet pipe, (330) shown in Fig. 3 are connected to the reactor, institute
It states and is provided with casing 410 in evaporation tank 400, in the reactor outlet pipe access described sleeve pipe 410, set in described sleeve pipe 410
There is aperture.The substance of reactor discharge is discharged into evaporation tank 400 by the dispersion of multiple apertures.
In accordance with an embodiment of the present disclosure, the size and shape of casing 410 without limitation, for example, the diameter of casing 410 can be with
42~50mm, wall thickness can be 4~6mm, and shape can be straight tube, be also possible to helix tube.Aperture size for example can be directly
High-velocity fluid is mainly obtained resolution and dispersion, slow release pressure by the aperture on outlet by 2~3mm of diameter, effect.
Referring back to Fig. 3.It is described to be provided with cooling interior bucket 350, institute from separation outer barrel 320 according to the embodiment of the present disclosure
The inside that condenser pipe 323 is set to the cooling interior bucket 350 is stated, the condensation reservoir 322 is formed in the bottom of the cooling interior bucket 350
Portion is provided with multiple ducts 351 on the bucket wall of the cooling interior bucket 350.Cooling below with reference to Fig. 5, to the embodiment of the present disclosure
Interior bucket is described.
Fig. 5 diagrammatically illustrates the schematic diagram of the cooling interior bucket 510 according to the embodiment of the present disclosure.
As shown in figure 5, multiple ducts 513 are provided on the bucket wall of cooling interior bucket 510, for the steaming for evaporating in evaporation tank
Vapour enters cooling interior bucket 510.
According to embodiments of the present invention, cooling water can be filled with into the condenser pipe 511 in cooling interior bucket 510 (such as by entering
Mouth 5111 is filled with, and is discharged from outlet 5112) so that the temperature in cooling interior bucket 510 is low relative to the temperature in evaporation tank, condensation
The temperature of steam can be reduced after 511 water-filling of pipe.
According to the embodiment of the present disclosure, for example, the water vapour evaporated in evaporation tank, oxygen and carbon dioxide can be from bucket walls
The multiple ducts 513 being arranged enter cooling interior bucket 510, and as shown by the arrows in Figure 5 flows up direction.Steam encounters cold air
Afterwards, condensation generates droplet and falls into condensation reservoir 512, is then discharged from leakage fluid dram 514.And oxygen and carbon dioxide can be from tops
The exhaust outlet 515 in portion is discharged.
According to an embodiment of the invention, the volume of condensation reservoir 512 is without limitation.For example, the volume of condensation reservoir 512 can be
50L~500L can be connect in condensation reservoir 512 with external circulating line by more radiation pipelines, and water transmitting ability can be
800kg/h~8000kg/h.Condenser pipe 511 can be horizontal wrap spiral cooling tube, and size is without limitation.
According to an embodiment of the invention, there are multiple 513 supplied gas of duct to pass through on bucket wall, cooling interior bucket 510 can make
100 DEG C or more of water vapour is condensed into 60 DEG C~90 DEG C of water, condensing capacity can be 200kg/h~2000kg/h.It is cooling
The volume in coil pipe area without limitation, such as volume can be returned with 1000L, condensed water in overcritical water oxidization reactor it is multiple
With can also otherwise utilized or direct emission.
Fig. 6 diagrammatically illustrates the flow chart of the method for processing organic wastewater according to the embodiment of the present disclosure.
As shown in fig. 6, this method includes operation S610~S640.
In operation S610, reactor is heated.
In operation S620, when the temperature in reactor enclosure body reaches the first temperature, start blender, and by the first solution
By the way that in the organic matter feed inlet input reactor shell, oxidant is passed through the oxidant feed mouth input reactor shell
In vivo, until the temperature in reactor enclosure body reaches second temperature.
In operation S630, when the pressure in reactor enclosure body reaches predetermined pressure, the back of reactor discharge outlet is opened
Pressure valve.
In operation S640, organic wastewater is passed through in organic matter feed inlet input reactor shell, in supercritical water environment
Under be oxidized, and from discharge port be discharged.
According to the embodiment of the present disclosure, for example, first reactor can be made full of water using the pre- thermal reactor of electric heating cover
Temperature in reactor enclosure body reaches the first temperature, such as can be 300 DEG C.In accordance with an embodiment of the present disclosure, the first solution example
It such as can be sucrose solution, by adjusting the ratio of sucrose solution and water, be stepped up sucrose concentration, sucrose solution is passed through into oxygen
In compound entrance input reactor, while oxidant is inputted to reactor.According to the embodiment of the present disclosure, which for example can be with
It is oxygen.Under conditions of 300 DEG C, oxidant and sucrose, which react, generates heat, continues to be heated to for temperature of reactor
Two temperature.
The embodiment of the present disclosure can effectively improve supercritical water reaction room temperature using sucrose solution.Different from propyl alcohol, sugarcane
Sugar aqueous solution is non-combustible and explosive articles, while the combustion heat of dense aqueous sucrose solution is higher than the combustion heat of propyl alcohol, can be faced super
Boundary's water reaction zone temperature is increased to 550 DEG C -800 DEG C of certain temperature section.
Due to the liner through aluminising, shot-peening hammering and spraying thermal barrier coating processing that the embodiment of the present disclosure provides, reaction
Device can bear higher temperature compared to existing technologies, and the service life of reactor can extend 5-10.According to the disclosure
Embodiment, the second temperature are not less than 600 DEG C.Preferably, the second temperature is between 650 DEG C to 800 DEG C, the temperature
Range is high compared to reaction temperature for the relevant technologies of other supercritical water reactions, effectively increases reaction speed.Also, by
In reaction temperature height, 10 times lower than conventional supercritical fluid water the time required to reaction, so that the volume of the equipment of same treatment ability is big
Width is reduced.
In accordance with an embodiment of the present disclosure, in the case where reaching reaction condition, for example, supercritical water oxidation temperature is maintained at
650 DEG C~750 DEG C, in the case that pressure is maintained at 20~25Mpa, start organic matter feeding device.Under general operating condition, reactor
Liner is 650 DEG C~800 DEG C close to oxidant feed mouth portion temperature, and corresponding reactor shell portion temperature is no more than 600
℃。
According to the embodiment of the present disclosure, the overcritical water oxidization reactor further includes cooling device, the reactor shell
The second area of first area and the close discharge port including the close organic matter feed inlet, the method also includes
The heating device and the cooling device are controlled, controls the temperature of the first area within a predetermined range, and control
The temperature for making the second area makes the temperature of the effluent of the discharge port be not less than 120 DEG C.
For example, can control the temperature of first area between 650 DEG C~800 DEG C.When organic concentration is higher, release
The heat of oxidation it is more, need at this time by cooling device to reactor cool down, make first area temperature control 800 DEG C with
It is interior.On the other hand, under cooling effect of the reaction product through the fluid between apparatus for supercooling and liner and shell, temperature is reduced to
120 DEG C~300 DEG C, optionally, the temperature of the effluent of discharge port can be between 150 DEG C to 300 DEG C.Relative to existing skill
60 DEG C or so of temperature of reactor discharge port in art, the temperature of the discharge port of the embodiment of the present disclosure is higher, such as can achieve
300 DEG C, the cooling burden of supercritical water reaction device is alleviated, equipment volume is reduced, while efficiency can be improved.
According to the embodiment of the present disclosure, the reactor further includes blender, and the stirrer configuration has ammeter and voltage
Table is respectively used to detect the electric current and voltage of the blender, and the method also includes the electric currents and/or electricity in the blender
When pressure reaches predetermined value, the feed rate of at least one of the organic matter feed inlet and oxidant feed mouth is reduced.
According to the embodiment of the present disclosure, the supercritical water oxidation system further includes monitoring system, and the method also includes sound
It should be controlled following at least one: the pressure of oxide feed in user's input or in response to the monitoring result of the monitoring system
And/or flow；The pressure and/or flow of organic matter feed；The temperature of the reactor and/or the evaporation tank；And/or
The state of the counterbalance valve.The description above for device is please referred to, details are not described herein again.
It will be understood by those skilled in the art that the feature recorded in each embodiment and/or claim of the disclosure can
To carry out multiple combinations and/or combination, even if such combination or combination are not expressly recited in the disclosure.Particularly, exist
In the case where not departing from disclosure spirit or teaching, the feature recorded in each embodiment and/or claim of the disclosure can
To carry out multiple combinations and/or combination.All these combinations and/or combination each fall within the scope of the present disclosure.
Although the disclosure, art technology has shown and described referring to the certain exemplary embodiments of the disclosure
Personnel it should be understood that in the case where the spirit and scope of the present disclosure limited without departing substantially from the following claims and their equivalents,
A variety of changes in form and details can be carried out to the disclosure.Therefore, the scope of the present disclosure should not necessarily be limited by above-described embodiment,
But should be not only determined by appended claims, also it is defined by the equivalent of appended claims.
Claims (10)
1. a kind of supercritical water oxidation apparatus, including reactor, the reactor include:
Reactor shell is provided with oxidant feed mouth, organic matter feed inlet and discharge port in the reactor shell；
Heating device, for promoting the temperature in the reactor enclosure body；And
Blender, including shaft, the shaft pass through the reactor shell.
2. supercritical water oxidation apparatus according to claim 1, in which:
The shaft passes through the discharge port；
The stirrer configuration has ammeter and/or voltmeter；And/or
The reactor further includes cooling device, and the cooling device includes at least one be arranged in outside the reactor shell
Group coolant jacket, wherein the heating device includes at least one set of heating mantle being arranged in outside the reactor shell, described anti-
Answering device shell includes the second area of the first area and the close discharge port close to the oxidant feed mouth, described to add
Thermal is set to the outside of the first area, and the cooling device is set to the outside of the second area.
3. supercritical water oxidation apparatus according to claim 1, wherein the reactor shell includes the first end wall, side
Wall and second end wall opposite with the first end wall, the oxidant feed mouth are set to first end wall, the organic matter
Feed inlet is set to the side wall, and the discharge port is set to second end wall, the reactor further include:
Liner is set to second end wall, and extends to the direction of first end wall, and the discharge port is set in described
The inside of lining,
Wherein, the organic matter feed inlet is greater than the organic matter feed inlet and the second end at a distance from first end wall
The distance of wall,
Wherein, the interior laying-in aluminising, shot-peening hammering and spraying thermal barrier coating processing, the thermal barrier coating include being arranged alternately
Multiple aluminium layers and multiple alumina layers.
4. supercritical water oxidation apparatus according to claim 1, further includes:
From separation outer barrel, described to be provided with evaporation tank, condensation reservoir and condenser pipe from separation outer barrel, the reactor is set to institute
It states from the inside for separating outer barrel, wherein the evaporation tank is connected with the discharge port, in the evaporation tank and the discharge port
Between be equipped with counterbalance valve, the condensation reservoir is set to the top of the evaporation tank, and the condenser pipe is set to the condensation reservoir
Top, so that the liquid energy that the gas evaporated in the evaporation tank at the condenser pipe in liquefied situation, liquefies
It is enough to fall after rise into the condensation reservoir.
5. supercritical water oxidation apparatus according to claim 4, in which:
It is provided with cooling tube in the evaporation tank, slag-drip opening is provided in the evaporation tank, draining is provided in the condensation reservoir
Mouthful, it is described to be provided with exhaust outlet from the top of separation outer barrel；
Described to be provided with cooling interior bucket from separation outer barrel, the condenser pipe is set to the inside of the cooling interior bucket, described cold
Solidifying pond is formed in the bottom of the cooling interior bucket, is provided with multiple ducts on the bucket wall of the cooling interior bucket；And/or
The evaporation tank is connected to by reactor outlet pipe with the reactor, and casing is provided in the evaporation tank, described anti-
It answers in device outlet access described sleeve pipe, described sleeve pipe is equipped with aperture.
6. supercritical water oxidation apparatus according to claim 5, in which:
Temperature sensor is provided in the evaporation tank, in condensation reservoir, in reactor shell；
Pressure sensor is provided in the reactor enclosure body；
The slag-drip opening is provided with pH on-line monitoring meter；
The exhaust ports are provided with volatile organic matter on-line monitoring device；And/or
The discharge outlet is provided with COD on-line monitoring device.
7. a kind of method for processing organic wastewater handles organic wastewater, institute by supercritical water oxidation apparatus described in claim 1
The discharge outlet for stating overcritical water oxidization reactor is provided with counterbalance valve, which comprises
The reactor is heated；
When temperature in the reactor enclosure body reaches the first temperature, start the blender, and the first solution is passed through into institute
It states organic matter feed inlet to input in the reactor enclosure body, oxidant is inputted into the reactor by the oxidant feed mouth
In shell, until the temperature in the reactor enclosure body reaches second temperature, wherein the second temperature is not less than 600 DEG C；
When pressure in the reactor enclosure body reaches predetermined pressure, the counterbalance valve is opened；
The organic wastewater is inputted in the reactor enclosure body by the organic matter feed inlet, wherein the organic wastewater
It is oxidized under supercritical water environment, and is discharged from the discharge port.
8. according to the method described in claim 7, wherein,
For the second temperature between 650 DEG C to 800 DEG C, first solution includes sucrose solution, and the oxidant includes
Oxygen；And/or
The stirrer configuration has ammeter and voltmeter, is respectively used to detect the electric current and voltage of the blender, the side
Method further includes reducing the oxidant feed mouth and organic when the electric current and/or voltage of the blender reach predetermined value
The feed rate of at least one of object feed inlet.
9. according to the method described in claim 7, wherein, the overcritical water oxidization reactor further includes cooling device, described
Reactor shell includes the second area of the first area and the close discharge port close to the oxidant feed mouth, described
Method further include:
Control the heating device and the cooling device, make the first area temperature control within a predetermined range, with
And the temperature of the control second area makes the temperature of the effluent of the discharge port not less than 120 DEG C, wherein the discharge port
Effluent temperature between 150 DEG C to 300 DEG C.
10. according to the method described in claim 7, wherein, the supercritical water oxidation apparatus further includes separating outer barrel certainly, described
Evaporation tank, condensation reservoir and condenser pipe are provided with from separation outer barrel, the reactor is set to the inside from separation outer barrel,
Wherein, the evaporation tank is connected with the discharge port, and counterbalance valve is equipped between the evaporation tank and the discharge port, described cold
Solidifying pond is set to the top of the evaporation tank, and the condenser pipe is set to the top of the condensation reservoir, steams in the evaporation tank
The gas of hair is at the condenser pipe in liquefied situation, and liquid can be fallen after rise into the condensation reservoir, the overcritical water oxygen
It further includes monitoring system that makeup, which is set, and the method also includes in response to user's input or in response to the monitoring knot of the monitoring system
Fruit controls following at least one:
The pressure and/or flow of oxide feed；
The pressure and/or flow of organic matter feed；
The temperature of the reactor and/or the evaporation tank；And/or
The state of the counterbalance valve.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910108899.1A CN109851131B (en) | 2019-02-03 | 2019-02-03 | Supercritical water oxidation device and organic wastewater treatment method |
| PCT/CN2020/073315 WO2020156337A1 (en) | 2019-02-03 | 2020-01-20 | Supercritical water all-in-one machine and organic wastewater treatment method |
| EP20747667.2A EP3919448A4 (en) | 2019-02-03 | 2020-01-20 | Supercritical water all-in-one machine and organic wastewater treatment method |
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|---|---|---|---|
| CN201910108899.1A CN109851131B (en) | 2019-02-03 | 2019-02-03 | Supercritical water oxidation device and organic wastewater treatment method |
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| CN109851131A true CN109851131A (en) | 2019-06-07 |
| CN109851131B CN109851131B (en) | 2020-11-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020156337A1 (en) * | 2019-02-03 | 2020-08-06 | 中国原子能科学研究院 | Supercritical water all-in-one machine and organic wastewater treatment method |
| CN118108327A (en) * | 2024-04-09 | 2024-05-31 | 中核海瑞格科技有限公司 | Wet oxidation treatment device and method thereof |
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| CN101629028A (en) * | 2009-08-27 | 2010-01-20 | 北京科技大学 | Multifunctional alumina/metal micro-laminated coating |
| CN105152509A (en) * | 2015-09-10 | 2015-12-16 | 新奥科技发展有限公司 | Supercritical reactor, supercritical reaction system and supercritical treatment method of sludge |
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| US20080135496A1 (en) * | 2000-10-10 | 2008-06-12 | Christophe Joussot-Dubien | Device for supercritical water oxidation of materials |
| CN101629028A (en) * | 2009-08-27 | 2010-01-20 | 北京科技大学 | Multifunctional alumina/metal micro-laminated coating |
| CN105152509A (en) * | 2015-09-10 | 2015-12-16 | 新奥科技发展有限公司 | Supercritical reactor, supercritical reaction system and supercritical treatment method of sludge |
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| WO2020156337A1 (en) * | 2019-02-03 | 2020-08-06 | 中国原子能科学研究院 | Supercritical water all-in-one machine and organic wastewater treatment method |
| CN118108327A (en) * | 2024-04-09 | 2024-05-31 | 中核海瑞格科技有限公司 | Wet oxidation treatment device and method thereof |
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| CN109851131B (en) | 2020-11-10 |
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