CN108911107A - A kind of organic wastewater Supercritical water oxidation treatment device and method - Google Patents
A kind of organic wastewater Supercritical water oxidation treatment device and method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 128
- 238000009284 supercritical water oxidation Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012530 fluid Substances 0.000 claims abstract description 73
- 239000007800 oxidant agent Substances 0.000 claims abstract description 64
- 230000001590 oxidative effect Effects 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 231100000252 nontoxic Toxicity 0.000 claims description 5
- 230000003000 nontoxic effect Effects 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of organic wastewater Supercritical water oxidation treatment device and methods, it includes oxidant pump, First Heat Exchanger, the second heat exchanger, heater, mixer, reactor, high-pressure pump, booster pump, energy recycle device, high-pressure gas-liquid separator and low-pressure gas-liquid separator.Organic wastewater Supercritical water oxidation treatment device of the invention is recycled the pressure energy of reaction under high pressure fluid using energy recycle device, is greatly reduced and is carried out required energy consumption of pressurizeing to organic wastewater raw material.Organic wastewater supercritical water oxidation treatment method of the invention is other than sufficiently recycling heat and pressure energy, supercritical water oxidation is carried out using excessive oxidant technique, keep organic wastewater oxidation efficiency high, it is provided with high-pressure gas-liquid separator and oxygen-enriched recycling tail gas process simultaneously, further reduced operating cost.The present invention is suitble to be widely applied in the processing of organic wastewater supercritical water oxidation.
Description
Technical field
The present invention relates to chemical industry and environmental protection technical field, at specifically a kind of organic wastewater supercritical water oxidation
Manage device and method.
Background technique
High concentration (COD COD>2000mg/L), toxic, organic wastewater with difficult degradation thereby processing is to generally acknowledge both at home and abroad
Technical problem.Traditional Technologies for Organic Wastewater Treatment (such as materializing strategy technology, biologic treating technique, wet oxidation, burning
Deng) there are at high cost, degradation rate is low, easily derivative secondary pollution problems.Supercritical water oxidation (Supercritical Water
Oxidation, SCWO) as a kind of novel processing organic wastewater technology, it is one of the method for effectively solving this problem;
Supercritical water oxidation be be more than water critical point (PC=22.1MPa, TC=374 DEG C) high-temperature and high-pressure conditions under, with
The method that air or other oxidants aoxidize organic matter.Supercritical water (supercritical water, SCW) conduct
One kind of supercritical fluid, compared with common liquid water and steam, the various physicochemical properties of supercritical water have occurred very big
Variation.The main physical parameter of SCW such as density, viscosity, ionic product and dielectric constant are decreased obviously, and diffusion coefficient is higher, are passed
Matter performance is good, can dissolve each other completely with gas (such as oxygen, nitrogen) and most organic matters, gas liquid film disappears, and eliminates
The reaction rate of interphase mass transfer resistance, dissolution wherein substance is no longer limited by mass transport process, is formed uniform phase system, is reacted
Speed is greatly speeded up.Within the even several seconds residence times less than 1 minute, the rapid combustion oxidation of 99.9% or more organic matter
At CO2、H2O and other nontoxic end products.Reaction temperature generally at 400-650 DEG C, avoids SO2, NOx, dioxin
The generation of equal secondary pollutions.Entire combustion oxidation process generates a large amount of heat, has biggish heat recovery potentiality, when organic
When amount of substance concentration reaches 3% or more, so that it may maintain reaction required temperature by autoxidation heat release in reaction process, not need
Extraneous heat supply, waste heat can recycle;
SCWO technology is compared with traditional method for processing organic wastewater, with oxidation reaction is thorough, removal rate is high, reaction unit volume
The series of advantages such as small, achievable autothermal reaction, are known as one of most promising environmental treatment method.But in order to realize super face
The high-temperature high-voltage reaction condition of boundary's water oxygen needs to expend huge energy, and in current supercritical water oxidation system, and one
As high-pressure fluid is directly down to by normal pressure by counterbalance valve, then carry out the separation of gas-liquid product, the pressure energy that fluid has is direct
Loss, cause energy significant wastage, as patent CN105130081A, CN105152248A, CN1730414A,
CN104671388A etc., if can sufficiently recycle this partial pressure energy, energy-saving effect will be considerable.Patent
CN104445573A discloses a kind of Novel supercritical water oxygen total system and processing method, is provided with pressure energy and recycles
And the energy recovery units such as waste heat recycling, pressure energy recycling carry out pressure recovery using hydraulic turbine unit, belong to pressure energy and arrive
Mechanical energy arrives the conversion of pressure energy again, and energy recovery efficiency is lower.Patent CN105627814A discloses a kind of for overcritical
The intermediate medium heat-exchanger rig of water oxidative system is given the heat transfer of fluid after supercritical water oxidation using intermediate medium
Material before reaction preheats material using the heat of fluid after supercritical water oxidation, the pressure of intermediate medium
It is maintained by the desuperheat water pump for counterbalance valve and moisturizing the branch setting being arranged on surge tank, can efficiently utilize fluid after reaction
Heat, but this method pressure energy using very limited.Based on this, it is necessary in view of the above-mentioned problems, developing one kind can be efficient
Using the thermal energy of reacting fluid, and it can effectively recycle the supercritical water oxidation treatment method of reaction under high pressure fluid pressure energy.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of organic wastewater Supercritical water oxidation treatment device and method,
The pressure energy of reacting fluid can be effectively recycled, the thermal energy of reacting fluid is efficiently utilized, system energy consumption can be greatly reduced, saves fortune
Row expense.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A kind of organic wastewater Supercritical water oxidation treatment device, it includes oxidant pump, First Heat Exchanger, the second heat exchanger, adds
Hot device, mixer, reactor, high-pressure pump, booster pump, energy recycle device, high-pressure gas-liquid separator and low-pressure gas-liquid separator,
The oxidant pump import is connect with oxidant supply pipeline, and the oxidant pump outlet enters with the First Heat Exchanger oxidant
Mouth connection, the First Heat Exchanger oxidant outlet are connect with the mixer, the First Heat Exchanger thermal fluid inlet and institute
State the connection of reactor fluid outlet line, the First Heat Exchanger hot fluid outlet ports and the high-pressure gas-liquid separator suction line
Connection, organic wastewater pipeline are divided into branch and lower branch, and the upper branch is connect with the high pressure pump inlet, the lower branch
It is connect with the energy recycle device low-pressure fluid entrance, the energy recycle device charging fluid outlet is pumped into the pressurization
Mouthful connection, the energy recycle device pressure release fluid outlet connect with the low-pressure gas-liquid separator inlet, the high-pressure pump with
The booster pump outlet is connect by pipeline with the second heat exchanger organic wastewater entrance, and the second exchanger heat fluid enters
Mouth is connect with the reactor fluid outlet line, and the second exchanger heat fluid outlet enters with the high-pressure gas-liquid separator
Mouth pipeline connection, the second heat exchanger organic wastewater outlet are connect through the heater with the mixer, the high pressure gas
Liquid/gas separator gaseous phase outlet is connect with the mixer, and the high-pressure gas-liquid separator liquid-phase outlet is divided into the first branch and second
Branch, the first branch are connect with the energy recycle device high pressure fluid entrances, the second branch by relief valve with
The low-pressure gas-liquid separator inlet pipeline connection, the mixer outlet are connect with the reactor inlet, the reactor
Fluid outlet is divided into third branch and the 4th branch, and the third branch is connect with the First Heat Exchanger thermal fluid inlet, institute
The 4th branch is stated to connect with the second exchanger heat fluid inlet.
As restriction, the oxidant pump is high-pressure plunger pump or compressor.
It is limited as another kind, the reactor is tubular reactor, membrane type cooling wall reactor or evaporation wall reactor.
It is limited as another kind, the First Heat Exchanger and second heat exchanger are wall-type heat exchange equipment.
It is limited as another kind, the heater uses electric heating, fuel Heating or gas heating form.
It is limited as another kind, the energy recycle device is centrifugal energy recycle device or positive displacement energy regenerating
Device.
A kind of organic wastewater supercritical water oxidation treatment method, specifically comprises the following steps：
（1）Organic wastewater to be processed is divided into branch and lower branch, and upper branch enters high-pressure pump and is pressurized, and lower branch enters energy
Amount recyclable device carries out being converted into high pressure organic wastewater after pressure energy exchanges with high-pressure fluid, and high pressure organic wastewater passes through booster pump
Pressurization converges with the pressurized organic wastewater of upper branch, converge it is latter with after the preheating of the second heat exchanger into mixer, together
When, oxidant also enters mixer after the pressurization of oxidant plenum pump, the pre-heat treatment；
（2）Enter reactor through the mixed material of mixer, in the reactor, the pollutant in organic wastewater is oxidized to
CO2、H2The nontoxic product such as O and inorganic salts；
（3）Reactor fluid outlet is divided into third branch and the 4th branch, third branch flow to First Heat Exchanger to oxidant into
Row preheating, the 4th branch flow to the second heat exchanger and preheats to organic wastewater, the two-way fluid after heat exchange cooling together into
Enter high-pressure gas-liquid separator；
（4）Into high-pressure gas-liquid separator fluid after gas-liquid separation, gas phase returns to mixer and recycles, liquid-phase outlet point
For the first branch and second branch, the first branch enters energy recycle device, and second branch enters low-pressure gas-liquid by relief valve
Separator；
（5）First branch liquid phase into energy recycle device is exchanged with lower branch organic wastewater progress pressure energy, and low pressure is had
Machine waste water is converted into high pressure organic wastewater, and high pressure liquid phase fluid is converted into low-pressure fluid, the low-pressure fluid after conversion with through pressure release
The second branch liquid phase of valve decompression enters low-pressure gas-liquid separator together, forms tail gas and liquid phase after the separation of low-pressure gas-liquid separator
Water does further recycling.
As restriction, step（1）Described in oxidant be one of hydrogen peroxide, ozone, pure oxygen or air, the oxygen
1-10 times of theoretical oxygen demand when the dosage of agent is useless Organic substance in water complete oxidation.
It is limited as another kind, step（1）Described in oxidant pump be high-pressure plunger pump or compressor, oxidant warp
Pressure is 22MPa-40MPa after crossing the oxidant plenum pump pressurization.
It is limited as another kind, step（1）Described in lower branch organic wastewater account for the 60%-90% of organic wastewater total flow.
It is limited as another kind, step（1）Described in upper branch organic wastewater through the pressurized pressure of the high-pressure pump be
22MPa-40MPa。
It is limited as another kind, step（1）Described in lower branch organic wastewater handed over through the energy recycle device pressure energy
20MPa-37MPa is pressurized to after changing.
It is limited as another kind, step（1）Described in high pressure organic wastewater 22MPa- is pressurized to by the booster pump
40MPa。
It is limited as another kind, step（1）In second heat exchanger preheating after, organic wastewater enter mixer before set
Heater is set, the heater is one kind of electric heating, fuel Heating or gas heating form, organic exhaust gas control temperature after heating
Degree is at 380 DEG C -700 DEG C.
It is limited as another kind, step（1）Described in reactor be tubular reactor, membrane type cooling wall reactor or evaporation
Wall reactor.
It is limited as another kind, step（2）Described in the operating condition of reactor be：Pressure 22MPa-40MPa, temperature
380 DEG C -700 DEG C, residence time 10s-600s.
It is limited as another kind, step（3）Described in First Heat Exchanger and second heat exchanger set for wall-type heat exchange
It is standby, it is preheated after oxidant and organic wastewater temperature be 300 DEG C -600 DEG C.
It is limited as another kind, step（4）Described in high-pressure gas-liquid separator gas phase be rich in N2And O2Gas and warp
The mixer is returned in the reactor and is further utilized as oxidant.
It is limited as another kind, step（4）Described in first branch liquid phase account for the 60%-90% of liquid phase total flow.
It is limited as another kind, step（5）Described in energy recycle device be centrifugal energy recycle device or positive displacement
Formula energy recycle device.
The present invention is due to using above-mentioned structure, and compared with prior art, acquired technological progress is：
（1）Organic wastewater Supercritical water oxidation treatment device of the invention is directed to the high-temperature high-voltage reaction condition of supercritical water oxidation
The huge problem of energy consumption is recycled the pressure energy of reaction under high pressure fluid using energy recycle device, recovery efficiency up to 90% or more,
It greatly reduces and required energy consumption of pressurizeing is carried out to organic wastewater raw material；
（2）Organic wastewater Supercritical water oxidation treatment device of the invention uses reverse-flow evaporation wall reactor, evaporation wall knot
Structure avoids salts substances in the deposition of reactor wall, reduces resultants in reaction process to the corrosivity of equipment, extending device makes
Use the service life；
（3）Organic wastewater supercritical water oxidation treatment method of the invention carries out supercritical water oxidation using excessive oxidant technique
Reaction, organic wastewater oxidation efficiency is high, the pollutant in organic wastewater sufficiently can be oxidized to CO2、H2The nothings such as O and inorganic salts
Malicious harmless products, and organic wastewater supercritical water oxidation treatment method setting high-pressure gas-liquid separator and oxygen-enriched tail of the invention
Gas reuse process, utilizes CO under condition of high voltage2And O2Dissolubility difference realizes the oxygen-enriched efficient reuse of tail gas, reduces operating cost；
（4）Organic wastewater supercritical water oxidation treatment method of the invention be capable of handling various concentration, it is toxic, it is difficult oxidation it is organic
The effective ways of waste water, organic removal rate is up to 99% or more in waste water, when organic matter mass concentration reaches in processing waste water
When 3% or more, reactor can reach oxidation heat self-balancing.
To sum up, organic wastewater Supercritical water oxidation treatment device of the invention, which greatly reduces, carries out organic wastewater raw material
Energy consumption needed for pressurization, while resultants in reaction process is reduced to the corrosivity of equipment；Organic wastewater supercritical water of the invention
Oxidation treatment method not only can sufficiently recycle heat and pressure energy, moreover it is possible to keep organic wastewater oxidation efficiency high, by setting
High-pressure gas-liquid separator and oxygen-enriched recycling tail gas process are set, further reduced operating cost.The present invention is suitble in organic wastewater
It is widely applied in supercritical water oxidation processing.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with the embodiment of the present invention
It is used to explain the present invention, is not construed as limiting the invention together.
Fig. 1 is the structural schematic diagram of organic wastewater Supercritical water oxidation treatment device described in the embodiment of the present invention.
In figure：1, oxidant；2, oxidant pump；3, First Heat Exchanger；4, mixer；5, the second heat exchanger；6, heater；
7, reactor；8, organic wastewater；9, high-pressure pump；10, booster pump；11, energy recycle device；12, high-pressure gas-liquid separator；13,
Relief valve；14, low-pressure gas-liquid separator；15, tail gas；16, liquid phase water；17, inorganic salts deslagging；18, upper branch；19, lower branch；
20, third branch；21, the 4th branch；22, the first branch；23, second branch.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is further explained.In the following detailed description, only pass through explanation
Mode describes certain exemplary embodiments of the invention.Undoubtedly, those skilled in the art will recognize,
In the case where without departing from the spirit and scope of the present invention, described embodiment can be repaired with a variety of different modes
Just.Therefore, attached drawing and description are regarded as illustrative in nature, and are not intended to limit the scope of the claims.
Embodiment 1
As shown in Figure 1, it includes oxidant pump 2, according to the organic wastewater Supercritical water oxidation treatment device of the present embodiment 1
One heat exchanger 3, the second heat exchanger 5, heater 6, mixer 4, reactor 7, high-pressure pump 9, booster pump 10, energy recycle device
11, high-pressure gas-liquid separator 12 and low-pressure gas-liquid separator 14,2 import of oxidant pump are connect with 1 supply pipeline of oxidant, oxidation
2 outlet of agent pump is connect with 3 oxidant inlet of First Heat Exchanger, and 3 oxidant outlet of First Heat Exchanger is connect with mixer 4, and first
3 thermal fluid inlet of heat exchanger is connect with 7 fluid outlet pipeline of reactor, 3 hot fluid outlet ports of First Heat Exchanger and high-pressure gas-liquid point
It is connected from 12 suction line of device, 8 pipeline of organic wastewater is divided into branch 18 and lower branch 19, upper branch 18 and 9 entrance of high-pressure pump
Connection, lower branch 19 are connect with 11 low-pressure fluid entrance of energy recycle device, the outlet of 11 charging fluid of energy recycle device and increasing
The connection of 10 entrance of press pump, 11 pressure release fluid outlet of energy recycle device are connect with 14 entrance of low-pressure gas-liquid separator, 9 He of high-pressure pump
The outlet of booster pump 10 is connect by pipeline with 5 organic wastewater entrance of the second heat exchanger, 5 thermal fluid inlet of the second heat exchanger with react
The connection of 7 fluid outlet pipeline of device, 5 hot fluid outlet ports of the second heat exchanger are connect with 12 suction line of high-pressure gas-liquid separator, and second
5 organic wastewater of heat exchanger exports heated device 6 and connect with mixer 4, and 12 gaseous phase outlet of high-pressure gas-liquid separator and mixer 4 connect
It connects, 12 liquid-phase outlet of high-pressure gas-liquid separator is divided into the first branch 22 and second branch 23, and the first branch 22 and energy regenerating fill
The connection of 11 high pressure fluid entrances is set, second branch 23 is connect by relief valve 13 with 14 suction line of low-pressure gas-liquid separator, is mixed
The outlet of clutch 4 is connect with 7 entrance of reactor, and 7 fluid outlet of reactor is divided into third branch 20 and the 4th branch 21, third branch
20 connect with 3 thermal fluid inlet of First Heat Exchanger, and the 4th branch 21 is connect with 5 thermal fluid inlet of the second heat exchanger.
In this way, the organic wastewater Supercritical water oxidation treatment device of the present embodiment 1 is high for the high temperature of supercritical water oxidation
The huge problem of reaction condition energy consumption is pressed, is recycled the pressure energy of reaction under high pressure fluid using energy recycle device 11, recovery efficiency
Up to 90% or more, greatly reduces and required energy consumption of pressurizeing is carried out to 8 raw material of organic wastewater.
In the present embodiment 1, oxidant pump 2 is high-pressure plunger pump or compressor.
At this point, oxidant pump 2 can be chosen according to 1 form of oxidant, it is right for the preferred high-pressure plunger pump of liquid oxidizer 1
In 1 preferred compressed machine of gaseous oxidizer.
In the present embodiment 1, reactor 7 is tubular reactor, membrane type cooling wall reactor or evaporation wall reactor.
Wherein, reactor 7 can be autoclave or tubular type, can be tubular reactor, membrane type cooling wall reactor or evaporation
One of wall reactor.It is preferred that reverse-flow evaporation wall overcritical water oxidization reactor, reacts by using reverse-flow evaporation wall
Device, evaporation wall construction avoid salts substances in the deposition of 7 wall of reactor, reduce corrosion of the resultants in reaction process to equipment
Property, extend service using life.Wherein, inorganic salts deslagging 17 is discharged from 7 outlet of reactor.
In the present embodiment 1, First Heat Exchanger 3 and the second heat exchanger 5 are wall-type heat exchange equipment.
At this point, First Heat Exchanger 3, the second heat exchanger 5 are wall-type heat exchange equipment, specially shell-and-tube, board-like, bushing type
One of with jacket type, preferred shell-and-tube tubular heat exchanger.
In the present embodiment 1, heater 6 is using electric heating, fuel Heating or gas heating form.
In the present embodiment 1, energy recycle device 11 is that centrifugal energy recycle device or positive displacement energy regenerating fill
It sets.
At this point, preferable valve-regulated positive displacement energy recycle device.
Embodiment 2
According to the organic wastewater supercritical water oxidation treatment method of the present embodiment 2, specifically comprise the following steps：
（1）Organic wastewater 8 to be processed divides for upper branch 18 and lower branch 19, and upper branch 18 is pressurized into high-pressure pump 9, lower branch
Road 19 enters energy recycle device 11 and carries out being converted into high pressure organic wastewater, high pressure organic waste after pressure energy exchanges with high-pressure fluid
Water is pressurized by booster pump 10 to be converged with the pressurized organic wastewater of upper branch 18, is converged latter with pre- by the second heat exchanger 5
Enter mixer 4 after heat, meanwhile, oxidant 1 is pressurized by oxidant pump 2, also enters mixer 4 after the pre-heat treatment；
（2）Enter reactor 7 through the mixed material of mixer 4, in reactor 7, the pollutant in organic wastewater 8 is oxidized
At CO2、H2The nontoxic product such as O and inorganic salts；
（3）7 fluid outlet of reactor is divided into third branch 20 and the 4th branch 21, and it is right that third branch 20 flow to First Heat Exchanger 3
Oxidant 1 is preheated, and the 4th branch 21 flow to the second heat exchanger 5 and preheats to organic wastewater, two after heat exchange cooling
Road fluid enters high-pressure gas-liquid separator 12 together；
（4）Into high-pressure gas-liquid separator 12 fluid after gas-liquid separation, gas phase return mixer 4 recycle, liquid phase goes out
Mouth is divided into the first branch 22 and second branch 23, and the first branch 22 enters energy recycle device 11, and second branch 23 passes through pressure release
Valve 13 enters low-pressure gas-liquid separator 14；
（5）22 liquid phase of the first branch into energy recycle device 11 is exchanged with lower 19 organic wastewater of branch progress pressure energy, will
Low pressure organic wastewater is converted into high pressure organic wastewater, and high pressure liquid phase fluid is converted into low-pressure fluid, the low-pressure fluid after conversion with
23 liquid phase of second branch being depressured through relief valve 13 enters low-pressure gas-liquid separator 14 together, after low-pressure gas-liquid separator 14 separates
It forms tail gas 15 and liquid phase water 16 does further recycling.
At this point, carrying out supercritical water oxidation by using 1 technique of excessive oxidant, 8 oxidation efficiency of organic wastewater is high,
The pollutant in organic wastewater 8 sufficiently can be oxidized to CO2、H2The nontoxic product such as O and inorganic salts, and the present embodiment 2
Organic wastewater supercritical water oxidation treatment method setting high-pressure gas-liquid separator 12 and oxygen-enriched recycling tail gas process, utilize high pressure
Under the conditions of CO2And O2Dissolubility difference realizes the oxygen-enriched efficient reuse of tail gas, reduces operating cost.
In the present embodiment 2, step（1）Middle oxidant 1 is one of hydrogen peroxide, ozone, pure oxygen or air, oxidation
1-10 times of theoretical oxygen demand when the dosage of agent 1 is useless Organic substance in water complete oxidation.
At this point, theoretical oxygen demand is 2-5 times when the dosage of preferred oxidant 1 is useless Organic substance in water complete oxidation.
In the present embodiment 2, step（1）Middle oxidant pump 2 is high-pressure plunger pump or compressor, and oxidant 1 is through peroxidating
Pressure is 22MPa-40MPa after 2 pressurization of agent pump.
In this way, oxidant pump 2 can be chosen according to 1 form of oxidant, it is right for the preferred high-pressure plunger pump of liquid oxidizer 1
In 1 preferred compressed machine of gaseous oxidizer, 1 increased pressure of preferred oxidant is 25MPa -35MPa.
In the present embodiment 2, step（1）In lower 19 organic wastewater of branch account for the 60%-90% of 8 total flow of organic wastewater.
At this point, it is preferred that it is 70%-80% that lower 19 organic wastewater of branch, which accounts for 8 total flow of organic wastewater,.Wherein, organic wastewater 8 is total
Flow is the summation of the first branch 22 and 23 organic wastewater of second branch.
In the present embodiment 2, step（1）In upper 18 organic wastewater of branch through the pressurized pressure of high-pressure pump 9 be 22MPa-
40MPa。
At this point, it is preferred that going up 18 organic wastewater of branch through the pressurized pressure of high-pressure pump 9 is 25MPa -35MPa.
In the present embodiment 2, step（1）In lower 19 organic wastewater of branch increase after the exchange of 11 pressure energy of energy recycle device
It is depressed into 20MPa-37MPa.
At this point, it is preferred that lower 19 organic wastewater of branch is pressurized most 23 MPa- after the exchange of 11 pressure energy of energy recycle device
32MPa。
In the present embodiment 2, step（1）Mesohigh organic wastewater is pressurized to 22MPa-40MPa by booster pump 10.
At this point, it is preferred that high pressure organic wastewater is pressurized to 25 MPa-35MPa by booster pump 10.
In the present embodiment 2, step（1）In the second heat exchanger 5 preheating after, organic wastewater enter mixer 4 before be arranged
Heater 6, heater 6 are one kind of electric heating, fuel Heating or gas heating form, and organic exhaust gas control temperature exists after heating
380℃-700℃。
Wherein, organic exhaust gas control temperature is at 450 DEG C -600 DEG C after preferably heating.
In the present embodiment 2, step（1）Middle reactor 7 is that tubular reactor, membrane type cooling wall reactor or evaporation wall are anti-
Answer device.
Wherein, reactor 7 can be autoclave or tubular type, can be tubular reactor, membrane type cooling wall reactor or evaporation
One of wall reactor.It is preferred that reverse-flow evaporation wall overcritical water oxidization reactor, reacts by using reverse-flow evaporation wall
Device, evaporation wall construction avoid salts substances in the deposition of 7 wall of reactor, reduce corrosion of the resultants in reaction process to equipment
Property, extend service using life.
In the present embodiment 2, step（2）The operating condition of middle reactor 7 is：Pressure 22MPa-40MPa, 380 DEG C of temperature-
700 DEG C, residence time 10s-600s.
Wherein, the operating condition of preferred reactor 7 is：25 MPa-35MPa of pressure, 450 DEG C -600 DEG C of temperature, when stop
Between 30 s -300s.
In the present embodiment 2, step（3）Middle First Heat Exchanger 3 and the second heat exchanger 5 are wall-type heat exchange equipment, through pre-
Oxidant 1 and 8 temperature of organic wastewater after heat are 300 DEG C -600 DEG C.
Wherein, oxidant 1 and 8 temperature of organic wastewater after preferably preheated are 350 DEG C -500 DEG C.
In the present embodiment 2, step（4）The gas phase of mesohigh gas-liquid separator 12 is rich in N2And O2Gas and through mixed
It is further utilized in 4 Returning reactor 7 of clutch as oxidant 1.
In the present embodiment 2, step（4）Middle 22 liquid phase of the first branch accounts for the 60%-90% of liquid phase total flow.
Wherein, preferably 22 liquid phase of the first branch accounts for the 70%-80% of liquid phase total flow
In the present embodiment 2, step（5）Middle energy recycle device 11 is that centrifugal energy recycle device or positive displacement energy return
Receiving apparatus.
At this point, preferable valve-regulated positive displacement energy recycle device.Centrifugal energy recycle device is former using water conservancy turbine
Reason completes energy transmission after " pressure energy-mechanical energy-pressure energy " conversion, and energy recovery efficiency is about 50%-70%；Normotopia
Shifting formula energy recycle device is converted using positive displacement working principle by " pressure energy-pressure energy ", has higher energy
Recovery efficiency can reach 90% or more
Therefore, the organic wastewater supercritical water oxidation treatment method of the present embodiment 2 is to be capable of handling various concentration, toxic, difficult oxygen
Change the effective ways of organic wastewater 8, organic removal rate is up to 99% or more in waste water, when organic matter quality is dense in processing waste water
When degree reaches 3% or more, reactor 7 can reach oxidation heat self-balancing.The present invention is suitble in the overcritical water oxygen of organic wastewater
It is widely applied in change processing.
The foregoing is merely the schematical specific embodiment of the present invention, the range being not intended to limit the invention.It is any
Those skilled in the art, the equivalent changes and modifications made under the premise of not departing from design and the principle of the present invention,
It should belong to the scope of protection of the invention.
Claims (20)
1. a kind of organic wastewater Supercritical water oxidation treatment device, it is characterised in that：It include oxidant pump, First Heat Exchanger,
Second heat exchanger, heater, mixer, reactor, high-pressure pump, booster pump, energy recycle device, high-pressure gas-liquid separator and low
It calms the anger liquid/gas separator, the oxidant pump import is connect with oxidant supply pipeline, the oxidant pump outlet and described first
The connection of heat exchanger oxidant inlet, the First Heat Exchanger oxidant outlet are connect with the mixer, the First Heat Exchanger
Thermal fluid inlet is connect with the reactor fluid outlet line, the First Heat Exchanger hot fluid outlet ports and the high-pressure gas-liquid
The connection of separator inlet pipeline, organic wastewater pipeline are divided into branch and lower branch, the upper branch and the high pressure pump inlet
Connection, the lower branch are connect with the energy recycle device low-pressure fluid entrance, and the energy recycle device charging fluid goes out
Mouth is connect with the pressurization pump intake, and the energy recycle device pressure release fluid outlet and the low-pressure gas-liquid separator inlet connect
It connecing, the high-pressure pump and the booster pump outlet are connect by pipeline with the second heat exchanger organic wastewater entrance, and described the
Two exchanger heat fluid inlets are connect with the reactor fluid outlet line, the second exchanger heat fluid outlet with it is described
The connection of high-pressure gas-liquid separator suction line, the second heat exchanger organic wastewater outlet is through the heater and the mixer
Connection, the high-pressure gas-liquid separator gaseous phase outlet are connect with the mixer, the high-pressure gas-liquid separator liquid-phase outlet point
For the first branch and second branch, the first branch is connect with the energy recycle device high pressure fluid entrances, and described second
Branch is connect by relief valve with the low-pressure gas-liquid separator inlet pipeline, the mixer outlet and the reactor inlet
Connection, the reactor fluid outlet are divided into third branch and the 4th branch, the third branch and First Heat Exchanger heat
Fluid inlet connection, the 4th branch are connect with the second exchanger heat fluid inlet.
2. a kind of organic wastewater Supercritical water oxidation treatment device according to claim 1, it is characterised in that：The oxidation
Agent pump is high-pressure plunger pump or compressor.
3. a kind of organic wastewater Supercritical water oxidation treatment device according to claim 1, it is characterised in that：The reaction
Device is tubular reactor, membrane type cooling wall reactor or evaporation wall reactor.
4. a kind of organic wastewater Supercritical water oxidation treatment device according to claim 1, it is characterised in that：Described first
Heat exchanger and second heat exchanger are wall-type heat exchange equipment.
5. a kind of organic wastewater Supercritical water oxidation treatment device according to claim 1, it is characterised in that：The heating
Device uses electric heating, fuel Heating or gas heating form.
6. a kind of organic wastewater Supercritical water oxidation treatment device according to claim 1, it is characterised in that：The energy
Recyclable device is centrifugal energy recycle device or positive displacement energy recycle device.
7. a kind of organic wastewater supercritical water oxidation treatment method, it is characterised in that：Specifically comprise the following steps：
（1）Organic wastewater to be processed is divided into branch and lower branch, and upper branch enters high-pressure pump and is pressurized, and lower branch enters energy
Amount recyclable device carries out being converted into high pressure organic wastewater after pressure energy exchanges with high-pressure fluid, and high pressure organic wastewater passes through booster pump
Pressurization converges with the pressurized organic wastewater of upper branch, converge it is latter with after the preheating of the second heat exchanger into mixer, together
When, oxidant also enters mixer after the pressurization of oxidant plenum pump, the pre-heat treatment；
（2）Enter reactor through the mixed material of mixer, in the reactor, the pollutant in organic wastewater is oxidized to
CO2、H2The nontoxic product such as O and inorganic salts；
（3）Reactor fluid outlet is divided into third branch and the 4th branch, third branch flow to First Heat Exchanger to oxidant into
Row preheating, the 4th branch flow to the second heat exchanger and preheats to organic wastewater, the two-way fluid after heat exchange cooling together into
Enter high-pressure gas-liquid separator；
（4）Into high-pressure gas-liquid separator fluid after gas-liquid separation, gas phase returns to mixer and recycles, liquid-phase outlet point
For the first branch and second branch, the first branch enters energy recycle device, and second branch enters low-pressure gas-liquid by relief valve
Separator；
（5）First branch liquid phase into energy recycle device is exchanged with lower branch organic wastewater progress pressure energy, and low pressure is had
Machine waste water is converted into high pressure organic wastewater, and high pressure liquid phase fluid is converted into low-pressure fluid, the low-pressure fluid after conversion with through pressure release
The second branch liquid phase of valve decompression enters low-pressure gas-liquid separator together, forms tail gas and liquid phase after the separation of low-pressure gas-liquid separator
Water does further recycling.
8. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in oxidant be one of hydrogen peroxide, ozone, pure oxygen or air, the dosage of the oxidant is useless Organic substance in water
1-10 times of theoretical oxygen demand when complete oxidation.
9. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in oxidant pump be high-pressure plunger pump or compressor, the oxidant by the oxidant plenum pump pressurization after pressure be
22 MPa-40MPa。
10. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in lower branch organic wastewater account for the 60%-90% of organic wastewater total flow.
11. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in upper branch organic wastewater through the pressurized pressure of the high-pressure pump be 22 MPa-40MPa.
12. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in lower branch organic wastewater be pressurized to 20 MPa -37MPa after energy recycle device pressure energy exchange.
13. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in high pressure organic wastewater 22 MPa-40MPa are pressurized to by the booster pump.
14. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
In after second heat exchanger preheating, organic wastewater heater is set before entering mixer, the heater is electric heating, combustion
One kind of oil heating or gas heating form, organic exhaust gas controls temperature at 380 DEG C -700 DEG C after heating.
15. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（1）
Described in reactor be tubular reactor, membrane type cooling wall reactor or evaporation wall reactor.
16. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（2）
Described in the operating condition of reactor be：Pressure 22MPa-40MPa, 380 DEG C -700 DEG C of temperature, residence time 10s-600s.
17. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（3）
Described in First Heat Exchanger and second heat exchanger be wall-type heat exchange equipment, it is preheated after oxidant and organic waste water temperature
Degree is 300 DEG C -600 DEG C.
18. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（4）
Described in high-pressure gas-liquid separator gas phase be rich in N2And O2Gas and return to conduct in the reactor through the mixer
Oxidant further utilizes.
19. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（4）
Described in first branch liquid phase account for the 60%-90% of liquid phase total flow.
20. a kind of organic wastewater supercritical water oxidation treatment method according to claim 7, it is characterised in that：Step（5）
Described in energy recycle device be centrifugal energy recycle device or positive displacement energy recycle device.
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