CN108217909B - Subcritical/supercritical catalytic oxidizer for dangerous wastewater - Google Patents
Subcritical/supercritical catalytic oxidizer for dangerous wastewater Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 226
- 239000002351 wastewater Substances 0.000 title claims abstract description 156
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 214
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 158
- 230000003647 oxidation Effects 0.000 claims abstract description 142
- 230000005284 excitation Effects 0.000 claims abstract description 102
- 239000002918 waste heat Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000010815 organic waste Substances 0.000 claims abstract description 31
- 230000001939 inductive effect Effects 0.000 claims abstract description 17
- 239000002920 hazardous waste Substances 0.000 claims abstract description 11
- 230000006698 induction Effects 0.000 claims description 61
- 230000001105 regulatory effect Effects 0.000 claims description 41
- 238000005485 electric heating Methods 0.000 claims description 37
- 238000002347 injection Methods 0.000 claims description 30
- 239000007924 injection Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 22
- 230000009471 action Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 13
- 238000009284 supercritical water oxidation Methods 0.000 description 12
- 239000002699 waste material Substances 0.000 description 10
- 231100001261 hazardous Toxicity 0.000 description 9
- 238000004321 preservation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000149 chemical water pollutant Substances 0.000 description 3
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- 238000005260 corrosion Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- -1 alicyclic hydrocarbon Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3228—Units having reflectors, e.g. coatings, baffles, plates, mirrors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The subcritical/supercritical catalytic oxidizer for dangerous waste water mainly comprises an excitation inducing device, a catalytic oxidizer feeding device, a catalytic oxidation device, a waste heat utilization device and a water quality on-line monitor, wherein the water outlet end of the excitation inducing device is communicated with the second water inlet end of the catalytic oxidation device, the outlet end of the catalytic oxidizer feeding device is communicated with the first water inlet end of the catalytic oxidation device, the high-temperature water outlet end of the waste heat utilization device is communicated with the water inlet end of the excitation inducing device, the high-temperature water outlet end of the waste heat utilization device is also communicated with the first water inlet end of the catalytic oxidation device, the water outlet end of the catalytic oxidation device is communicated with the high-temperature water inlet end of the waste heat utilization device, and the water quality on-line monitor is arranged at the low-temperature water outlet end of the waste heat utilization device. The method adopts the pre-heated hazardous waste water to split, heats and excites and activates organic waste in part of the hazardous waste water to induce the reaction of the hazardous waste water, and then combines the flow to induce the integral reaction, so that the method has the advantages of high starting speed, less energy consumption and mild reaction conditions.
Description
Technical Field
The invention relates to the technical field of water pollution control, in particular to a subcritical/supercritical catalytic oxidizer for dangerous wastewater.
Background
Hazardous waste water produced in the production and manufacturing processes of chemical industry, electronic industry, printing and dyeing industry, mechanical industry and medicine industry and waste reagents or laboratory liquid are complex in components, often contain high-concentration polycyclic aromatic hydrocarbon compounds, heterocyclic compounds, polychlorinated biphenyls, various isomers and other nondegradable organic wastes, halogenated hydrocarbon, alicyclic hydrocarbon and other organic solvents or phthalate ester-containing organic solvents and various oily waste water, cyanide-containing acute toxic substances, phenols-containing acute toxic substances and other chronic toxic substances, even trinitrotoluene and other flammable and explosive substances, are extremely easy to cause serious environmental pollution, and threaten human health. The traditional biochemical method has extremely low degradation efficiency on dangerous wastewater, and the conventional incineration method has high treatment cost and is easy to produce secondary pollution.
Supercritical water oxidation (supercritical water oxidation, SCWO) is a process in which water is oxidized in supercritical (T>374.15℃，P>22.12 MPa). Under the action of high temperature and high pressure, active oxygen and C-H bond react to generate free radical HO 2 It forms H with H in organics 2 O 2 Further forming HO, reacting the free radical HO with high activity and strong oxidizing ability with organic matter to generate organic free radical R, reacting the organic free radical R with active oxygen and organic matter to finally generate CO 2 、H 2 O and other substances, and S, cl, P and other elements are oxidized to generate sulfate, chloride, phosphate and other salts, and metal ions are converted into oxides. The supercritical water oxidation technology has obvious advantages in the aspect of treating general dangerous waste water, particularly dangerous waste water containing more difficult-to-degrade organic matters, but firstly, the reaction is carried out at high temperature and high pressure, the energy consumption required for starting is high, a large amount of energy is also required for supplying in the oxidation reaction process to ensure that the reaction is continuously and stably carried out, secondly, the treatment efficiency of dangerous waste water containing a large amount of difficult-to-degrade aromatic hydrocarbon compounds is low, the dangerous waste water is difficult to completely decompose to reach the standard as desired, if the simple increase of the temperature and the pressure also cause barriers to the requirements and the safety of equipment materials, meanwhile, the corrosion to a reactor is serious at the ultra-high temperature, and the popularization and the application of the supercritical water oxidation treatment technology are objectively influenced.
Chinese patent 201110121462.5 provides a supercritical water oxidation equipment system utilizing auxiliary fuel to supply heat, comprising a reactor, a material device in communication with a material inlet on an end cap of the reactor, an oxidant device in communication with an oxidant inlet on the end cap of the reactor, a desalination device in communication with a solid salt outlet at the bottom of the reactor, and a fuel supply device and a cooling water device. The system is heated by utilizing electric energy, and the auxiliary fuel (methanol easy to decompose) and landfill leachate are directly mixed and then burnt in a reactor (the high temperature section of the system reaches more than 800 ℃) to supply energy to ensure the stable operation of the system, but firstly, the auxiliary fuel (methanol) easy to decompose is needed, so that the fuel cost is directly increased, the processing capacity of organic matters is increased, and secondly, the temperature of 800 ℃ is too high, so that the material and the use safety of the equipment are doubtful; and the problems of high energy consumption of integral heating start-up, severe requirements of high-temperature corrosion on reaction equipment and the like are also existed. Chinese patent 201410267877.7 provides a supercritical water oxidation treatment system for printing and dyeing wastewater and sludge, which comprises a concentration pretreatment device, a supercritical water oxidation device, an oxidant (liquid oxygen) supply device and a wastewater recovery system, wherein the supercritical oxidation device comprises an auxiliary heating type supercritical water oxidation reactor, a methanol starting preheater, a methanol preheater and a waste liquid preheater, and utilizes heat generated by methanol combustion to heat and start and ensure the reaction temperature of supercritical oxidation of the printing and dyeing wastewater, but has the problems of large equipment investment, high reaction temperature and low reaction speed of unused catalyst, and also directly and indirectly increases the problems of high wastewater treatment cost, high overall heating starting energy consumption and the like by utilizing methanol heating. Chinese patent 201610997137.8 provides a method for cooperatively treating organic waste liquid and heavy metal waste liquid by supercritical water, which comprises the steps of filling the organic waste liquid and the heavy metal waste liquid into a reaction kettle, raising the temperature of the reaction kettle to 400-700 ℃, raising the pressure to 20-30MPa, enabling the waste liquid to react in a supercritical state, cooling to room temperature and reducing the pressure to normal pressure, and discharging residual liquid, wherein the problems of intermittent treatment of a treatment system, extremely low heat utilization efficiency, long treatment time, high running cost and the like exist. Chinese patent 201010267595.9 provides a method for treating high-concentration landfill leachate by catalytic supercritical water oxidation, which is characterized in that landfill leachate is conveyed into a supercritical water oxidation reactor (the temperature is 100-450 ℃) by a high-pressure pump, oxygen and a catalyst are introduced to enable complete catalytic oxidation reaction of the leachate, and then a gas-liquid mixture after the reaction is cooled and separated, wherein the reaction speed is improved by using the catalyst, but the oxygen and the catalyst are introduced at the same time, and the problems of no recycling of waste heat after the reaction, extremely low heat utilization efficiency, high overall heating start energy consumption, pure oxygen supply and the like exist.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the background technology and providing the energy-saving environment-friendly type dangerous wastewater subcritical/supercritical catalytic oxidizer which can be started with low energy consumption, is used for exciting, activating and inducing oxidation reaction of part of waste liquid and activating and catalyzing oxidation of most of waste liquid waste heat, and has the advantages of mild reaction conditions and high oxidation efficiency.
The technical scheme adopted for solving the technical problems is as follows: the subcritical/supercritical catalytic oxidizer for dangerous waste water mainly comprises an excitation inducing device, a catalytic oxidizer feeding device, a catalytic oxidation device, a waste heat utilization device and a water quality on-line monitor, wherein the water outlet end of the excitation inducing device is communicated with the second water inlet end of the catalytic oxidation device, the outlet end of the catalytic oxidizer feeding device is communicated with the first water inlet end of the catalytic oxidation device, the high-temperature water outlet end of the waste heat utilization device is communicated with the water inlet end of the excitation inducing device, the high-temperature water outlet end of the waste heat utilization device is also communicated with the first water inlet end of the catalytic oxidation device, the water outlet end of the catalytic oxidation device is communicated with the high-temperature water inlet end of the waste heat utilization device, and the water quality on-line monitor is arranged at the low-temperature water outlet end of the waste heat utilization device.
The excitation induction device comprises a shell I, an energy-saving electric heating assembly, a microwave excitation assembly and/or an ultraviolet excitation assembly; the energy-saving electric heating assembly is arranged on the inner wall or the outer wall of the shell I or a pipeline communicated with the shell I, and can rapidly heat dangerous waste water flowing through the excitation induction device and activate organic waste in the dangerous waste water, and the microwave excitation assembly and the ultraviolet excitation assembly are arranged on the outer wall of the shell I and can excite and activate the organic waste flowing through the excitation induction device and induce oxidation reaction of the organic waste;
the catalytic oxidizer feeding device comprises a storage tank and a metering pump, wherein the inlet end of the metering pump is communicated with the outlet end of the storage tank through a pipeline, and the outlet end of the metering pump is communicated with a pipeline connected with the high-temperature water outlet end of the waste heat utilization device and the first water inlet end of the catalytic oxidizer so as to realize the communication between the outlet end of the catalytic oxidizer feeding device and the first water inlet end of the catalytic oxidizer; pumping out the catalytic oxidant in the storage tank by the metering pump, mixing the catalytic oxidant with part of dangerous wastewater flowing out of the waste heat utilization device, and spraying the mixed wastewater into the catalytic oxidation device through the spraying pipe;
the catalytic oxidation device mainly comprises a shell II and an injection pipe, wherein the injection pipe is communicated with a first water inlet end of the catalytic oxidation device and is fixed in the shell II and is a straight pipe or an annular pipe, and the injection pipe is provided with injection holes so as to be beneficial to uniformly mixing the mixed liquid of the injected catalytic oxidant and part of dangerous waste water with the dangerous waste water which is excited by the excitation induction device, and the catalytic oxidation reaction is rapidly generated;
The waste heat utilization device is preferably a heat exchanger, and is used for recovering heat of high-temperature water treated by the catalytic oxidation device, preheating dangerous wastewater before treatment, and reducing the overall energy consumption of the system; after preheating, part of dangerous waste water enters an excitation induction device, and the other part of dangerous waste water is mixed with the catalytic oxidant pumped by a catalytic oxidant meter feeding device and then enters a catalytic oxidation reaction device;
the water quality on-line monitor adopts a mature sewage discharge detection instrument, and the water quality of the treated dangerous wastewater is monitored in real time through on-line water sample collection and analysis and data collection and control, so that the standard discharge is ensured.
Further, the energy-saving type electric heating component is an energy-saving ceramic electric heating element or an energy-saving quartz electric heating element which can be heated rapidly.
The microwave excitation component mainly comprises a microwave generation element and a microwave output element, wherein the microwave generation element is connected with the microwave output element, and microwaves generated by the microwave generation element are transmitted into dangerous wastewater through the microwave output element, so that polar molecules in the dangerous wastewater generate high-frequency oscillation, activate organic wastes and induce oxidation reaction of the organic wastes.
The ultraviolet light excitation component mainly comprises an ultraviolet light generation element and a reflection output element, wherein the ultraviolet light generation element is connected with the reflection output element, and ultraviolet light generated by the ultraviolet light generation element is directionally injected into dangerous waste water under the action of the reflection output element, so that electrons in the dangerous waste water are transited from a low energy level to a high energy level, the activity of organic waste is excited, and the oxidation reaction of the organic waste is induced.
Further, the excitation induction device further comprises a three-way regulating valve, the water inlet end of the three-way regulating valve is communicated with the high-temperature water outlet end of the waste heat utilization device, the water outlet end of the three-way regulating valve is respectively communicated with the first water inlet end of the catalytic oxidation device and the water inlet end of the energy-saving electric heating assembly, and the three-way regulating valve is used for controlling the temperature in the catalytic oxidation device through proportion distribution of water.
Further, the excitation inducing device may further include a solar heating assembly including a solar light collecting element and a solar heat collecting element, the solar light collecting element being disposed in sunlight, the solar energy being concentrated to the solar heat collecting element by using a convex lens light concentrating characteristic; the solar heat collecting element is arranged on the outer wall of the excitation inducing device, and light energy collected by the solar light collecting element is converted into heat energy required by high-pressure dangerous waste liquid.
Further, a catalyst is arranged in the shell I of the excitation induction device and used for accelerating the progress of excitation activation and induction oxidation reaction of the microwave and ultraviolet light on the organic waste. The catalyst may be supported on a catalyst support and mounted in the housing I, or may be coated on the inner surface of the housing I, or may be otherwise disposed in the housing I. The catalyst may be TiO 2 Etc.
Furthermore, the catalytic oxidation device can be further provided with more than one cyclone plate, the cyclone plate is fixed on the inner wall of the shell II and positioned behind the jet pipe, and the cyclone plate is spiral, so that dangerous wastewater and mixed liquid of the dangerous wastewater and the catalytic oxidation agent are quickly and uniformly mixed and then enter a main reaction zone of the catalytic oxidation device, and catalytic oxidation reaction occurs in subcritical and/or supercritical states.
Further, the catalytic oxidation device and the excitation inducing device may share the same housing.
Further, the heat exchanger is a high-temperature and high-pressure resistant tubular or tube plate heat exchanger, and the heat exchanger can be one heat exchanger or a heat exchanger group formed by more than two heat exchangers.
Further, the subcritical/supercritical catalytic oxidizer for dangerous waste water further comprises an input/return device, the input/return device mainly comprises a high-pressure pump, an inlet end of the high-pressure pump is externally connected with a dangerous waste water inflow pipeline, the inlet end of the high-pressure pump is further communicated with a low-temperature water outlet end of the waste heat utilization device, an outlet end of the high-pressure pump is directly connected with the low-temperature water inlet end of the waste heat utilization device, and the input/return device is used for pumping dangerous waste water in a pressurizing mode and pumping the dangerous waste water which does not reach the standard back to the catalytic oxidation device for reprocessing.
Further, the subcritical/supercritical catalytic oxidizer for dangerous wastewater further comprises a heat preservation layer, wherein the heat preservation layer is wrapped outside the excitation induction device, the catalytic oxidation device and the waste heat recovery device, so that heat dissipation is prevented.
Further, the hazardous wastewater subcritical/supercritical catalytic oxidizer further comprises a bracket for mounting and fixing the device.
The specific working process of the invention is as follows:
preheating dangerous waste water: the normal temperature dangerous waste water is pressurized to 23-30MPa by a high pressure pump and enters a waste heat utilization device for preheating, a small part of the preheated dangerous waste water flows into an excitation induction device, a large part of the preheated dangerous waste water is mixed with the catalytic oxidant flowing out of a catalytic oxidant meter feeding device and flows into a catalytic oxidation device, and the distribution proportion of the dangerous waste water is adjusted in real time through a three-way regulating valve according to the temperature change in the catalytic oxidation device.
1. Heating, inducing/exciting dangerous waste water: and part of dangerous waste water is heated by an energy-saving electric heating component and/or a solar heating component in the excitation induction device, is excited and activated under the action of a microwave exciter and/or an ultraviolet light exciter, induces organic waste to react, and then flows into the catalytic oxidation device.
2. Catalytic oxidation reaction of hazardous waste water: the two dangerous waste water streams are rapidly mixed in a catalytic oxidation device, and catalytic oxidation exothermic reaction is carried out, so that toxic and harmful substances and organic waste are rapidly oxidized and degraded in subcritical and/or supercritical states, and the temperature in the catalytic oxidation device is kept at 300-500 ℃ in the reaction;
3. Heat exchange of hazardous waste water: the high-temperature water flowing out of the catalytic oxidation device exchanges heat with dangerous wastewater pumped into the waste heat utilization device from the high-pressure pump in the waste heat utilization device and then is reduced to 25-50 ℃;
4. discharging water reaching the standard: the effluent of the waste heat utilization device is monitored by a water quality on-line monitor, the water reaching the standard can be directly discharged or subjected to next-stage treatment, and the water not reaching the standard enters the catalytic oxidation device again for oxidative degradation.
The invention has the beneficial effects that:
1. the method has the advantages of quick starting speed, low energy consumption, mild reaction condition, high oxidative decomposition efficiency (particularly for the oxidative decomposition efficiency of the refractory aromatic compounds) of the organic wastes and quick reaction speed.
2. The dangerous waste water is catalyzed and oxidized by the catalytic oxidant under subcritical and/or supercritical conditions, so that the temperature and pressure required by the reaction are reduced, the oxidative decomposition capacity is improved, the operation time is shortened, the high-temperature corrosion is reduced, and the operation cost is reduced.
3. The method utilizes clean solar energy or energy-saving electric heating elements to heat dangerous wastewater, and self-heats heat released by oxidation combustion of organic wastes, and recycles waste heat after reaction, thereby saving conventional energy (electric energy), realizing recycling of heat energy and reducing environmental pollution.
4. The catalytic supercritical water oxidation technology is utilized to rapidly finish catalytic oxidation treatment of toxic and harmful and difficult-to-degrade dangerous wastewater in a closed environment, so that the reaction speed is high, the reaction time is short, the occupied area of equipment is small, the organic waste removal rate is high, and no secondary pollution is caused.
Drawings
FIG. 1 is a schematic diagram of a subcritical/supercritical catalytic oxidizer for hazardous wastewater in accordance with embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of a subcritical/supercritical catalytic oxidizer for hazardous wastewater in accordance with embodiment 2 of the present invention;
FIG. 3 is a schematic diagram of a subcritical/supercritical catalytic oxidizer for hazardous wastewater in accordance with embodiment 3 of the present invention;
FIG. 4 is a schematic diagram of a subcritical/supercritical catalytic oxidizer for hazardous wastewater in accordance with example 4 of the present invention;
in the figure: 1-excitation inducing means; 11-a shell I; 12-a three-way regulating valve; 13-an energy-saving electric heating component; 14-a microwave excitation assembly; 141—a microwave generating element; 142—a microwave output element; 15-an ultraviolet excitation assembly; 151-an ultraviolet light generating element; 152-a reflective output element; 16-a solar heating assembly; 161-a solar energy light collecting element; 162—a solar collector element; 17-a catalytic layer; 18-a temperature measuring instrument I; 19—a temperature measuring instrument ii; 2-a catalytic oxidation unit; 21-a shell II; 22-jet pipe; 23-a swirl plate; 24-a main reaction zone; 25-a pressure measuring instrument I; 26-a pressure measuring instrument II; 27-a temperature measuring instrument III; 3-a waste heat utilization device; 31-double pipe heat exchanger; 32-U-shaped tubular heat exchanger; 33-submerged coil heat exchanger; 34-a spiral wound tube type hollow heat exchanger; 35-a back pressure valve; 36-a three-way valve; 4-an online water quality monitor; 5-a catalytic oxidizer metering device; 51—a catalytic oxidant storage tank; 52-a metering pump; 6-an input/return means; 61-high pressure pump; 7, an insulating layer; 8-a bracket.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
Referring to fig. 1, a subcritical/supercritical catalytic oxidizer for dangerous wastewater mainly comprises an excitation induction device 1, a catalytic oxidation device 2, a waste heat utilization device 3, a water quality on-line monitor 4, a catalytic oxidizer feeding device 5, an input/reflux device 6, an insulating layer 7 and a bracket 8.
The excitation induction device 1 mainly comprises a shell I11, a three-way regulating valve 12, an energy-saving electric heating component 13 and a microwave excitation component 14, wherein the three-way regulating valve 12 is arranged on a pipeline outside a water inlet end of the excitation induction device 1, the water inlet end of the three-way regulating valve 12 is communicated with a high-temperature water outlet end of the waste heat utilization device 3 through a pipeline, two water outlet ends of the three-way regulating valve 12 are respectively communicated with the water inlet end of the energy-saving electric heating component 13 and a first water inlet end of the catalytic oxidation device 2 through pipelines, the water outlet end of the energy-saving electric heating component 13 is communicated with the inside of the shell I11, and the three-way regulating valve 12 regulates and controls the reaction temperature in the catalytic oxidation device 2 by regulating the water outlet proportion of the two water outlet ends; the energy-saving electric heating component 13 is fixed on the outer wall of the shell I11, heats dangerous waste water and activates organic waste; the microwave excitation assembly 14 is arranged on the outer wall of the shell I11 and comprises a microwave generation element 141 and a microwave output element 142, and microwaves generated by the microwave generation element 141 are led into dangerous waste water through the microwave output element 142 to excite and activate organic waste to induce the reaction of the organic waste; the water inlet end and the water outlet end of the excitation induction device 1 are respectively provided with a temperature measuring instrument I18 and a temperature measuring instrument II 19 which are respectively used for measuring the temperature of the dangerous waste water preheated by the waste heat utilization device 3 and the temperature of the dangerous waste water flowing out of the excitation induction device 1; the water outlet end of the excitation inducing device 1 is arranged on the shell I11.
The catalytic oxidation device 2 mainly comprises a shell II 21 and an injection pipe 22, wherein a second water inlet end of the catalytic oxidation device 2 is communicated with a water outlet end of the excitation induction device 1 through a pipeline, the injection pipe 22 is annular and fixed on the inner wall of the shell II 21, the injection pipe 22 is communicated with the first water inlet end of the catalytic oxidation device, and an injection hole for injecting a catalytic oxidant is formed in the injection pipe 22, so that dangerous wastewater and the catalytic oxidant are quickly and uniformly mixed and enter a main reaction zone 24 to perform catalytic oxidation reaction; the catalytic oxidation device 2 is also provided with a pressure measuring instrument I25, a temperature measuring instrument III 26 and a pressure measuring instrument II 27, which respectively measure the pressure of dangerous waste water entering the catalytic oxidation device 2 and the reaction temperature and pressure in the catalytic oxidation device 2.
The waste heat utilization device 3 comprises a double pipe heat exchanger 31, a back pressure valve 35 and a three-way valve 36, wherein the high Wen Jinshui end of the double pipe heat exchanger 31 is communicated with the water outlet end of the catalytic oxidation device 2 through a pipeline, and the low-temperature water inlet end of the double pipe heat exchanger 31 is communicated with the outlet end of the high-pressure pump 61 through a pipeline, so that heat exchange is carried out between high-temperature water and low-temperature dangerous waste water flowing out by the catalytic oxidation device 2, and the preheating of the dangerous waste water is realized; the back pressure valve 35 is communicated with the low-temperature water outlet end of the waste heat utilization device 3 through a pipeline, the constant pressure of the catalytic oxidation device 2 and the waste heat utilization device 3 is ensured, the water inlet end of the three-way valve 36 is communicated with the water outlet end of the back pressure valve 35, the two water outlet ends of the three-way valve 36 are respectively communicated with the high-pressure pump 61 and the external discharge pipeline, and water flow is led to the high-pressure pump 61 or the external discharge according to the monitoring result of the water quality on-line monitor 4.
The collection point of the water quality on-line monitor 4 is arranged on a pipeline between the water outlet end of the back pressure valve 35 and the water inlet end of the three-way valve 36, and is used for collecting and analyzing water quality on line so as to ensure standard discharge of dangerous wastewater; dangerous waste water which does not meet the discharge standard is pumped back to be subjected to catalytic oxidation treatment through the high-pressure pump 61.
The catalytic oxidizer feeding device 5 comprises a storage tank 51 and a metering pump 52, wherein the outlet end of the storage tank 51 is communicated with the inlet end of the metering pump 52 through a pipeline, and the outlet end of the metering pump 52 is communicated with the first water inlet end of the catalytic oxidizer 2 through a pipeline. The metering pump 52 pumps out the catalytic oxidizer in the storage tank 51 to be mixed with the preheated hazardous wastewater and then enter the catalytic oxidation device 2.
The input/return device 6 mainly comprises a high-pressure pump 61, wherein the inlet end of the high-pressure pump 61 is externally connected with a dangerous waste water inflow pipeline, and the high-pressure pump 61 pumps dangerous waste water flowing in from the dangerous waste water inflow pipeline or substandard dangerous waste water flowing out from the three-way valve 36 into the catalytic oxidation device for reaction.
The heat preservation layer 7 is wrapped outside the excitation induction device 1, the catalytic oxidation device 2 and the waste heat utilization device 3; the bracket 8 is used for mounting and fixing the device.
The working process comprises the following steps: the dangerous waste water flows into a pipeline through the dangerous waste water flowing into a high-pressure pump 61, the high-pressure pump 61 pressurizes the dangerous waste water to 28MPa, then preheats the dangerous waste water to 150 ℃ through a waste heat utilization device 3, part of the dangerous waste water enters an excitation induction device 1 under the action of a three-way regulating valve 12, the excitation induction device 1 heats the dangerous waste water through an energy-saving electric heating assembly 13 and activates and induces a reaction through microwave excitation generated by a microwave excitation assembly 14, and the dangerous waste water enters a catalytic oxidation device 2 after the temperature is raised to 300 ℃; part of the hazardous waste water is mixed with the catalytic oxidation agent pumped out from the storage tank 51 to form catalytic oxidation liquid, and then the catalytic oxidation liquid is sprayed into the catalytic oxidation device 2 through the spraying pipe 22. After the two parts of dangerous waste water are rapidly mixed in the catalytic oxidation device 2, the two parts of dangerous waste water are subjected to catalytic oxidation and degradation in a subcritical state; the high temperature water flowing out from the catalytic oxidation device 2 is cooled to normal temperature after heat exchange by the waste heat utilization device 3; the water flowing out from the low-temperature water outlet end of the waste heat utilization device 3 is collected and analyzed through the water quality on-line monitor 4, the water reaching the standard is discharged or is subjected to next-stage treatment, and the water not reaching the standard is pumped back to the catalytic oxidation device 2 through the high-pressure pump 61 for further treatment.
Example 2
Referring to fig. 2, a subcritical/supercritical catalytic oxidizer for dangerous wastewater mainly comprises an excitation induction device 1 and a catalytic oxidation device 2 which share the same shell, a waste heat utilization device 3, a water quality on-line monitor 4, a catalytic oxidizer feeding device 5, an input/reflux device 6, a heat preservation layer 7 and a bracket 8.
The excitation induction device 1 mainly comprises a shell I11, a three-way regulating valve 12, an energy-saving electric heating component 13, a microwave excitation component 14 and an ultraviolet excitation component 15, wherein the three-way regulating valve 12 is arranged on a pipeline outside the water inlet end of the excitation induction device 1, the water inlet end of the three-way regulating valve 12 is communicated with the high-temperature water outlet end of the waste heat utilization device 3 through a pipeline, the two water outlet ends of the three-way regulating valve 12 are respectively communicated with the water inlet end of the energy-saving electric heating component 13 and the catalytic oxidation device 2 through pipelines, the water outlet end of the energy-saving electric heating component 13 is communicated with the inside of the shell I11, and the three-way regulating valve 12 regulates and controls the reaction temperature in the catalytic oxidation device 2 by regulating the water outlet proportion of the two water outlet ends; the energy-saving electric heating component 13 is fixed on the outer wall of the shell I11, heats dangerous waste water and activates organic waste; the microwave excitation assembly 14 is arranged on the outer wall of the shell I11 and comprises a microwave generation element 141 and a microwave output element 142, and microwaves generated by the microwave generation element 141 are led into dangerous waste water through the microwave output element 142 to excite and activate organic waste to induce the reaction of the organic waste; the ultraviolet excitation assembly 15 is arranged on the outer wall of the shell I11 and comprises an ultraviolet light generating element 151 and an ultraviolet light output element 152, and microwaves generated by the ultraviolet light generating element 151 are led into dangerous waste water through the ultraviolet light output element 152 to excite the activity of organic wastes and induce the organic wastes to react; the water inlet end and the shell I11 of the excitation induction device 1 are respectively provided with a temperature measuring instrument I18 and a temperature measuring instrument II 19 which are respectively used for measuring the temperature of dangerous waste water which enters the excitation induction device 1 after being preheated by the waste heat utilization device 3 and the temperature of dangerous waste water which flows out of the excitation induction device 1.
The catalytic oxidation device 2 and the excitation induction device 1 share a shell I11, an injection pipe 22 is also arranged in the catalytic oxidation device 2, the injection pipe 22 is annular and fixed on the inner wall of the shell I11, the injection pipe 22 is communicated with a first water inlet end of the catalytic oxidation device, and an injection hole for injecting a catalytic oxidant is formed in the injection pipe 22, so that dangerous wastewater and the catalytic oxidant are quickly and uniformly mixed and enter a main reaction zone 24 to perform catalytic oxidation reaction; the catalytic oxidation device 2 is also provided with a pressure measuring instrument I25, a temperature measuring instrument III 26 and a pressure measuring instrument II 27, which respectively measure the pressure of dangerous waste water entering the catalytic oxidation device 2 and the reaction temperature and pressure in the catalytic oxidation device 2.
The waste heat utilization device 3 comprises a U-shaped tubular heat exchanger 32, a spiral wound tubular hollow tube heat exchanger 34, a back pressure valve 35 and a three-way valve 36, wherein the high Wen Jinshui end of the U-shaped tubular heat exchanger 32 is communicated with the water outlet end of the catalytic oxidation device 2, the low-temperature water inlet end of the U-shaped tubular heat exchanger 32 is communicated with a high-pressure pump 61 pipeline, the water inlet end of the spiral wound tubular hollow tube heat exchanger 34 is communicated with the water outlet end of the U-shaped tubular heat exchanger 32, and the spiral wound tubular heat exchanger 34 is wound on a shell outside the water outlet end of the catalytic oxidation device 2, so that heat exchange is carried out between high-temperature water flowing out by the catalytic oxidation device 2 and low-temperature dangerous waste water, and the aim of preheating dangerous waste water is achieved; the back pressure valve 35 is communicated with the low-temperature water outlet end of the waste heat utilization device 3 through a pipeline, the constant pressure of the catalytic oxidation device 2 and the waste heat utilization device 3 is ensured, the water inlet end of the three-way valve 36 is communicated with the water outlet end of the back pressure valve 35, the two water outlet ends of the three-way valve 36 are respectively communicated with the high-pressure pump 61 and the external discharge pipeline, and water flow is led to the high-pressure pump 61 or the external discharge according to the detection result of the water quality on-line monitor 4.
The collection point of the water quality on-line monitor 4 is arranged on a pipeline between the water outlet end of the back pressure valve 35 and the water inlet end of the three-way valve 36, and is used for collecting and analyzing water quality on line so as to ensure standard discharge of dangerous wastewater; dangerous waste water which does not meet the discharge standard is pumped back to be subjected to catalytic oxidation treatment through the high-pressure pump 61.
The catalytic oxidizer feeding device 5 comprises a storage tank 51 and a metering pump 52, wherein the outlet end of the storage tank 51 is communicated with the inlet end of the metering pump 52 through a pipeline, and the outlet end of the metering pump 52 is communicated with the first water inlet end of the catalytic oxidizer 2 through a pipeline. The metering pump 52 pumps out the catalytic oxidizer in the storage tank 51 to be mixed with the preheated hazardous wastewater and then enter the catalytic oxidation device 2.
The input/return device 6 mainly comprises a high-pressure pump 61, wherein the inlet end of the high-pressure pump 61 is externally connected with a dangerous waste water inflow pipeline, and the high-pressure pump 61 pumps dangerous waste water flowing in from the dangerous waste water inflow pipeline or dangerous waste water which does not reach standards and is conveyed by the three-way valve 36 into the catalytic oxidation device for reaction.
The heat preservation layer 7 is wrapped outside the excitation induction device 1, the catalytic oxidation device 2 and the waste heat utilization device 3; the bracket 8 is used for mounting and fixing the device.
The working process comprises the following steps: the dangerous waste water flows into a pipeline through the dangerous waste water flowing into a high-pressure pump 61, the high-pressure pump 61 pressurizes the dangerous waste water to 24MPa, the dangerous waste water is preheated to 300 ℃ through a waste heat utilization device 3, part of the dangerous waste water enters an excitation induction device 1 under the action of a three-way regulating valve 12, the excitation induction device 1 is heated and activated through an energy-saving electric heating assembly 13, and the microwave excitation assembly 14 and an ultraviolet excitation assembly 15 excite and activate and induce reactions, and the dangerous waste water enters a catalytic oxidation device 2 after the temperature is increased to 370 ℃; the other part is mixed with the catalyst oxide pumped from the storage tank 51 to form a catalyst oxide liquid, and then enters the catalytic oxidation apparatus 2 through the injection pipe 22. After the two waste solutions are quickly mixed, catalytic oxidation combustion is carried out under subcritical conditions to release heat, so that the reaction temperature is quickly raised to a supercritical state, and the waste solutions are quickly oxidized and degraded under the supercritical state; the high temperature water flowing out from the catalytic oxidation device 2 is cooled to normal temperature after heat exchange by the waste heat utilization device 3; and water flowing out from the low-temperature water outlet end of the waste heat utilization device 3 is collected and analyzed through the water quality on-line monitor 4, water reaching the standard is discharged or is subjected to next-stage treatment, and the water is treated again if the water does not reach the standard.
Example 3
Referring to fig. 3, a subcritical/supercritical catalytic oxidizer for dangerous wastewater mainly comprises an excitation induction device 1, a catalytic oxidation device 2, a waste heat utilization device 3, a water quality on-line monitor 4, a catalytic oxidizer feeding device 5, an input/reflux device 6, an insulating layer 7 and a bracket 8.
The excitation induction device 1 comprises a shell I11, a three-way regulating valve 12, an energy-saving electric heating component 13, an ultraviolet excitation component 15, a solar heating component 16 and a catalytic layer 17, wherein the three-way regulating valve 12 is arranged on a pipeline outside the water inlet end of the excitation induction device 1, the water inlet end of the three-way regulating valve 12 is communicated with the high-temperature water outlet end of the waste heat utilization device 3 through a pipeline, the two water outlet ends of the three-way regulating valve 12 are respectively communicated with the water inlet end of the energy-saving electric heating component 13 and the catalytic oxidation device 2 through pipelines, the water outlet end of the energy-saving electric heating component 13 is communicated with the inside of the shell I11, and the three-way regulating valve 12 regulates and controls the reaction temperature in the catalytic oxidation device 2 by regulating the water outlet proportion of the two water outlet ends; the energy-saving electric heating component 13 is fixed on the outer wall of the shell I11, heats dangerous waste water and activates organic waste; the ultraviolet excitation assembly 15 is arranged on the outer wall of the shell I11 and comprises an ultraviolet light generating element 151 and an ultraviolet light output element 152, and ultraviolet light generated by the ultraviolet light generating element 151 is led into dangerous wastewater through the ultraviolet light output element 152 to excite activity to induce reaction; the solar heating component 16 is arranged on the outer wall of the shell I11, the solar heating component 16 comprises a solar light collecting element 161 and a solar heat collecting element 162, the solar light collecting element 161 is placed under sunlight, solar energy is collected to the solar heat collecting element 162 by utilizing the condensation characteristic of a convex lens, and the solar heat collecting element is arranged on the outer wall of the shell I11, so that the light energy collected by the solar light collecting element is converted into heat energy required by heating high-pressure dangerous waste liquid; the catalytic layer 17 is arranged on the inner wall of the shell I11 and is used for accelerating the excitation induction speed of ultraviolet light; the water inlet end and the water outlet end of the excitation induction device 1 are respectively provided with a temperature measuring instrument I18 and a temperature measuring instrument II 19 which are respectively used for measuring the temperature of dangerous waste water which enters the excitation induction device 1 after being preheated by the waste heat utilization device 3 and the temperature of dangerous waste water which flows out of the excitation induction device 1.
The catalytic oxidation device 2 mainly comprises a shell II 21 and an injection pipe 22, wherein a second water inlet end of the catalytic oxidation device 2 is communicated with a water outlet end of the excitation induction device 1 through a pipeline, the injection pipe 22 is annular and fixed on the inner wall of the shell II 21, the injection pipe 22 is communicated with the first water inlet end of the catalytic oxidation device 2, and an injection hole for injecting a catalytic oxidant is formed in the injection pipe 22, so that dangerous wastewater and the catalytic oxidant are quickly and uniformly mixed and enter a main reaction zone 24 to perform catalytic oxidation reaction; the catalytic oxidation device 2 is also provided with a pressure measuring instrument I25, a temperature measuring instrument III 26 and a pressure measuring instrument II 27, which respectively measure the pressure of dangerous waste water entering the catalytic oxidation device 2 and the reaction temperature and pressure in the catalytic oxidation device 2.
The waste heat utilization device 3 comprises an immersed coil heat exchanger 33, a back pressure valve 35 and a three-way valve 36, wherein the high Wen Jinshui end of the immersed coil heat exchanger 33 is communicated with the water outlet end of the catalytic oxidation device 2, and the low-temperature water inlet end of the immersed coil heat exchanger 33 is communicated with a high-pressure pump 61 through a pipeline, so that heat exchange is carried out between high-temperature water and low-temperature dangerous wastewater flowing out from the catalytic oxidation device 2, and the preheating of the dangerous wastewater is realized; the back pressure valve 35 is communicated with the water outlet end of the immersed coil heat exchanger 33 through a pipeline, the constant pressure of the catalytic oxidation device 2 and the waste heat utilization device 3 is ensured, the water inlet end of the three-way valve 36 is communicated with the low-temperature water outlet end of the back pressure valve 35, the two water outlet ends of the three-way valve 36 are respectively communicated with the high-pressure pump 61 and the external pipeline, and water flow is led to the high-pressure pump 61 or the external pipeline according to the detection result of the water quality on-line monitor 4.
The collection point of the water quality on-line monitor 4 is arranged on a pipeline between the water outlet end of the back pressure valve 35 and the water inlet end of the three-way valve 36, and is used for collecting and analyzing water quality on line so as to ensure standard discharge of dangerous wastewater; dangerous waste water which does not meet the discharge standard is pumped back to be subjected to catalytic oxidation treatment through the high-pressure pump 61.
The catalytic oxidizer feeding device 5 comprises a storage tank 51 and a metering pump 52, wherein the outlet end of the storage tank 51 is communicated with the inlet end of the metering pump 52 through a pipeline, and the outlet end of the metering pump 52 is communicated with the first water inlet end of the catalytic oxidizer 2 through a pipeline. The metering pump 52 pumps out the catalytic oxidizer in the storage tank 51 to be mixed with the preheated hazardous wastewater and then enter the catalytic oxidation device 2.
The input/return device 6 mainly comprises a high-pressure pump 61, wherein the inlet end of the high-pressure pump 61 is externally connected with a dangerous waste water inflow pipeline, and the high-pressure pump 61 pumps dangerous waste water flowing in from the dangerous waste water inflow pipeline or substandard dangerous waste water flowing out from the three-way valve 36 into the catalytic oxidation device for reaction.
The heat preservation layer 7 is wrapped outside the excitation induction device 1, the catalytic oxidation device 2 and the waste heat utilization device 3; the bracket 8 is used for mounting and fixing the device.
The working process comprises the following steps: the dangerous waste water flows into a pipeline through the dangerous waste water and enters a high-pressure pump 61, the high-pressure pump 61 pressurizes the dangerous waste water to 27MPa, the dangerous waste water is preheated to 200 ℃ through a waste heat utilization device 3, part of the dangerous waste water enters an excitation induction device 1 under the action of a three-way regulating valve 12, the excitation induction device 1 is heated through a solar heating assembly 16 and/or an energy-saving electric heating assembly 13, ultraviolet light is used for excitation, activation and induction reaction, and the dangerous waste water enters a catalytic oxidation device 2 after the temperature is increased to 450 ℃; part of the mixture is mixed with the catalyst oxide pumped from the storage tank 51 to form a catalyst oxide liquid, and the catalyst oxide liquid enters the catalytic oxidation apparatus 2 through the injection pipe 22. After the two parts of dangerous waste water are rapidly mixed in the catalytic oxidation device 2, the two parts of dangerous waste water are subjected to catalytic oxidation and degradation in a supercritical state; the high temperature water flowing out from the catalytic oxidation device 2 is cooled to normal temperature after heat exchange by the waste heat utilization device 3; the effluent of the waste heat utilization device 31 is detected by the water quality on-line monitor 4, the effluent is discharged or subjected to the next stage of treatment, and the water which does not reach the standard is pumped back to the catalytic oxidation device 2 by the high-pressure pump 61 for further treatment.
Example 4
Referring to fig. 4, a subcritical/supercritical catalytic oxidizer for dangerous wastewater mainly comprises an excitation induction device 1 and a catalytic oxidation device 2 which share the same shell, a waste heat utilization device 3, a water quality on-line monitor 4, a catalytic oxidizer feeding device 5, an input/reflux device 6, a heat preservation layer 7 and a bracket 8.
The excitation induction device 1 comprises a shell I11, a three-way regulating valve 12, an energy-saving electric heating component 13, a microwave excitation component 14, a solar heating component 16 and a catalytic layer 17, wherein the three-way regulating valve 12 is arranged on a pipeline outside the water inlet end of the excitation induction device 1, the water inlet end of the three-way regulating valve 12 is communicated with the high-temperature water outlet end of the waste heat utilization device 3 through a pipeline, the two water outlet ends of the three-way regulating valve 12 are respectively communicated with the water inlet end of the energy-saving electric heating component 13 and the catalytic oxidation device 2 through pipelines, the water outlet end of the energy-saving electric heating component 13 is communicated with the inside of the shell I11, and the three-way regulating valve 12 regulates and controls the reaction temperature in the catalytic oxidation device 2 by regulating the water outlet proportion of the two water outlet ends; the energy-saving electric heating component 13 is fixed on the outer wall of the shell I11, heats dangerous waste water and activates organic waste; the microwave excitation assembly 14 is arranged on the outer wall of the shell I11 and comprises a microwave generation element 141 and a microwave output element 142, and microwaves generated by the microwave generation element 141 are led into dangerous waste water through the microwave output element 142 to excite the activity of organic wastes and induce the reaction of the organic wastes; the solar heating component 16 is arranged on the outer wall of the shell I11, the solar heating component 16 comprises a solar light collecting element 161 and a solar heat collecting element 162, the solar light collecting element 161 is placed under sunlight, solar energy is collected to the solar heat collecting element 162 by utilizing the condensation characteristic of a convex lens, and the solar heat collecting element is arranged on the outer wall of the shell I11, so that the light energy collected by the solar light collecting element is converted into heat energy required by heating high-pressure dangerous waste liquid; the water inlet end and the water outlet end of the excitation induction device 1 are also provided with a temperature measuring instrument I18 and a temperature measuring instrument II 19 which are respectively used for measuring the temperature of dangerous waste water which enters the excitation induction device 1 after being preheated by the waste heat utilization device 3 and the temperature of dangerous waste water which flows out of the excitation induction device 1.
The catalytic oxidation device 2 and the excitation induction device 1 share a shell I11, the catalytic oxidation device 2 further comprises an injection pipe 22 and 2 swirl plates 23, the injection pipe 22 fixed on the shell 11 is provided with injection holes for injecting a catalytic oxidant, the injection pipe 22 is communicated with a first water inlet end of the catalytic oxidation device, the swirl plates 23 are spirally fixed on the inner wall of the shell 11 and positioned behind the injection pipe 22, so that heated dangerous waste water and the catalytic oxidant are quickly and uniformly mixed and enter a main reaction zone 24 for catalytic oxidation reaction; the catalytic oxidation device 2 further comprises a pressure measuring instrument I25, a temperature measuring instrument III 26 and a pressure measuring instrument II 27, which respectively measure the pressure of dangerous waste water entering the catalytic oxidation device 2 and the temperature and the pressure in the catalytic oxidation device 2.
The waste heat utilization device 3 comprises a U-shaped tubular heat exchanger 32, a back pressure valve 35 and a three-way valve 36, wherein the high Wen Jinshui end of the U-shaped tubular heat exchanger 32 is communicated with the water outlet end of the catalytic oxidation device 2, and the low-temperature water inlet end is communicated with a high-pressure pump 61 pipeline, so that heat exchange is carried out between high-temperature water flowing out by the catalytic oxidation device 2 and low-temperature dangerous waste water to preheat the dangerous waste water; the low-temperature water inlet end of the U-shaped tubular heat exchanger 32 is communicated with a high-pressure pump 61 pipeline; the back pressure valve 35 is communicated with the low-temperature water outlet end of the waste heat utilization device through a pipeline, the constant pressure of the catalytic oxidation device 2 and the waste heat utilization device 3 is ensured, the water inlet end of the three-way valve 36 is communicated with the water outlet end of the back pressure valve 35, the two water outlet ends of the three-way valve 36 are respectively communicated with the high-pressure pump 61 and the external drainage pipeline, and water flow is led to the high-pressure pump 61 or the external drainage according to the detection result of the water quality on-line monitor 4.
The collection point of the water quality on-line monitor 4 is arranged on a pipeline between the water outlet end of the back pressure valve 35 and the water inlet end of the three-way valve 36, and is used for collecting and analyzing water quality on line so as to ensure standard discharge of dangerous wastewater; dangerous waste water which does not meet the discharge standard is pumped back to be subjected to catalytic oxidation treatment through the high-pressure pump 61.
The catalytic oxidizer feeding device 5 comprises a storage tank 51 and a metering pump 52, wherein the outlet end of the storage tank 51 is communicated with the inlet end of the metering pump 52 through a pipeline, and the outlet end of the metering pump 52 is communicated with the first water inlet end of the catalytic oxidizer 2 through a pipeline. The metering pump 52 pumps out the catalytic oxidizer in the storage tank 51 to be mixed with the preheated hazardous wastewater and then enter the catalytic oxidation device 2.
The input/return device 6 mainly comprises a high-pressure pump 61, wherein an inlet end of the high-pressure pump 61 is externally connected with a dangerous waste water inflow pipeline, and the high-pressure pump 61 pumps dangerous waste water flowing in from the dangerous waste water inflow pipeline or dangerous waste water which does not reach standards and flows out from the three-way valve 36 into the catalytic oxidation device for reaction.
The heat preservation layer 7 is wrapped outside the excitation induction device 1, the catalytic oxidation device 2 and the waste heat utilization device 3; the bracket 8 is used for mounting and fixing the device.
The working process comprises the following steps: the dangerous waste water enters a high-pressure pump 61 through a dangerous waste water inflow pipeline, the high-pressure pump 61 pressurizes the dangerous waste water to 25MPa, the dangerous waste water is preheated to 250 ℃ through a waste heat utilization device 3, part of the dangerous waste water enters an excitation induction device 1 under the action of a three-way regulating valve 12, the excitation induction device 1 is heated through a solar heating component, an energy-saving electric heating component 13 can be adopted for heating when the solar energy is insufficient, microwave excitation activation induction reaction is utilized, and the temperature is increased to 350 ℃; the other part is mixed with the catalytic oxidation agent pumped out of the storage tank 51 to form catalytic oxidation liquid, and the catalytic oxidation liquid enters the catalytic oxidation device 2; uniformly mixing the materials through a fixed cyclone plate 23, and carrying out catalytic oxidation combustion heat release under subcritical conditions, wherein the reaction temperature is rapidly increased to a supercritical state, so that the materials are rapidly oxidized and degraded under the supercritical state; the high temperature water flowing out from the catalytic oxidation device 2 is cooled to normal temperature after heat exchange by the waste heat utilization device 3; the effluent of the waste heat utilization device 3 is detected by a warp detector 4, discharged water reaching the standard or subjected to next-stage treatment, and treated again if the water does not reach the standard.
Claims (6)
1. The subcritical/supercritical catalytic oxidizer for dangerous waste water is characterized by mainly comprising an excitation induction device, a catalytic oxidizer feeding device, a catalytic oxidation device, a waste heat utilization device and a water quality on-line monitor, wherein the water outlet end of the excitation induction device is communicated with the second water inlet end of the catalytic oxidation device, the outlet end of the catalytic oxidizer feeding device is communicated with the first water inlet end of the catalytic oxidation device, the high-temperature water outlet end of the waste heat utilization device is communicated with the water inlet end of the excitation induction device, the high-temperature water outlet end of the waste heat utilization device is also communicated with the first water inlet end of the catalytic oxidation device, the water outlet end of the catalytic oxidation device is communicated with the high-temperature water inlet end of the waste heat utilization device, and the water quality on-line monitor is arranged at the low-temperature water outlet end of the waste heat utilization device;
The excitation induction device comprises a shell I, an energy-saving electric heating assembly, a microwave excitation assembly and/or an ultraviolet excitation assembly; the energy-saving electric heating component is arranged on the inner wall or the outer wall of the shell I or on a pipeline communicated with the shell I; the microwave excitation component and the ultraviolet excitation component are arranged on the outer wall of the shell I; the catalytic oxidizer feeding device comprises a storage tank and a metering pump, wherein the inlet end of the metering pump is communicated with the outlet end of the storage tank through a pipeline, and the outlet end of the metering pump is communicated with a pipeline connected with the high-temperature water outlet end of the waste heat utilization device and the first water inlet end of the catalytic oxidizer; the catalytic oxidation device mainly comprises a shell II and an injection pipe, wherein the injection pipe is communicated with a first water inlet end of the catalytic oxidation device and is fixed in the shell II and is a straight pipe or an annular pipe, and injection holes are formed in the injection pipe; the waste heat utilization device adopts a heat exchanger;
the excitation induction device also comprises a solar heating component, wherein the solar heating component comprises a solar light collecting element and a solar heat collecting element, and the solar light collecting element is arranged in sunlight; the solar heat collecting element is arranged on the outer wall of the excitation inducing device;
The excitation induction device further comprises a three-way regulating valve, the water inlet end of the three-way regulating valve is communicated with the high-temperature water outlet end of the waste heat utilization device, and the water outlet end of the three-way regulating valve is respectively communicated with the first water inlet end of the catalytic oxidation device and the water inlet end of the energy-saving electric heating assembly;
preheating dangerous waste water: the normal-temperature dangerous waste water is pressurized to 23-30MPa by a high-pressure pump and enters a waste heat utilization device for preheating, a small part of the preheated dangerous waste water flows into an excitation induction device, a large part of the preheated dangerous waste water is mixed with the catalytic oxidant flowing out of a catalytic oxidant meter feeding device and flows into a catalytic oxidation device, and the distribution proportion of the dangerous waste water is adjusted in real time through a three-way regulating valve according to the temperature change in the catalytic oxidation device; heating, inducing/exciting dangerous waste water: part of dangerous waste water is heated by an energy-saving electric heating component and/or a solar heating component in an excitation induction device, is excited and activated under the action of a microwave exciter and/or an ultraviolet light exciter, induces organic waste to react, and then flows into a catalytic oxidation device; catalytic oxidation reaction of hazardous waste water: the two dangerous waste water streams are rapidly mixed in a catalytic oxidation device, and catalytic oxidation exothermic reaction occurs, so that toxic and harmful substances and organic waste are rapidly oxidized and degraded in subcritical and/or supercritical states, and the temperature in the catalytic oxidation device is kept at 300-500 ℃ in the reaction.
2. The hazardous waste subcritical/supercritical catalytic oxidizer of claim 1, wherein the energy-saving electric heating assembly is an energy-saving ceramic electric heating element or an energy-saving quartz electric heating element capable of rapid heating.
3. The hazardous waste subcritical/supercritical catalytic oxidizer according to claim 1 or 2, wherein the microwave excitation assembly comprises mainly a microwave generating element and a microwave output element, the microwave generating element and the microwave output element being connected; the ultraviolet light excitation component mainly comprises an ultraviolet light generating element and a reflection output element, and the ultraviolet light generating element is connected with the reflection output element.
4. The subcritical/supercritical catalytic oxidizer for dangerous waste water according to claim 1 or 2, wherein the catalytic oxidizer is further provided with more than one swirl plate, and the swirl plate is fixed on the inner wall of the shell ii and positioned behind the jet pipe, and is in a spiral shape.
5. The subcritical/supercritical catalytic oxidizer of claim 1 or 2, wherein the excitation inducing device further comprises a three-way regulating valve, wherein the water inlet end of the three-way regulating valve is communicated with the high-temperature water outlet end of the waste heat utilization device, and the water outlet end of the three-way regulating valve is respectively communicated with the first water inlet end of the catalytic oxidizer and the water inlet end of the energy-saving electric heating assembly.
6. The hazardous waste water subcritical/supercritical catalytic oxidizer according to claim 1 or 2, further comprising an insulating layer, wherein the insulating layer is wrapped outside the excitation inducing device, the catalytic oxidation device and the waste heat recovery device.
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| CN109231793B (en) * | 2018-09-13 | 2020-11-17 | 西安交通大学 | Ecological toilet system taking subcritical hydrothermal liquefaction as core and method for treating excrement |
| CN112358026B (en) * | 2020-10-30 | 2024-01-23 | 西安理工大学 | Organic hazardous waste supercritical water reinforced oxidation treatment coupling power generation system |
| CN114985434B (en) * | 2022-06-06 | 2023-11-17 | 杭州坤灵环境技术有限公司 | Process for comprehensively utilizing subsequent substances and energy of organic residue hydrolysis treatment device |
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