CN112358026A - Organic hazardous waste supercritical water enhanced oxidation treatment coupling power generation system - Google Patents
Organic hazardous waste supercritical water enhanced oxidation treatment coupling power generation system Download PDFInfo
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- CN112358026A CN112358026A CN202011195014.5A CN202011195014A CN112358026A CN 112358026 A CN112358026 A CN 112358026A CN 202011195014 A CN202011195014 A CN 202011195014A CN 112358026 A CN112358026 A CN 112358026A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 238000010248 power generation Methods 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 230000008878 coupling Effects 0.000 title claims description 11
- 238000010168 coupling process Methods 0.000 title claims description 11
- 238000005859 coupling reaction Methods 0.000 title claims description 11
- 238000009284 supercritical water oxidation Methods 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000012530 fluid Substances 0.000 claims description 65
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000003860 storage Methods 0.000 claims description 32
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 30
- 239000002351 wastewater Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 239000010815 organic waste Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000010842 industrial wastewater Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 organic matters Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
- F01D15/10—Adaptations for driving, or combinations with, electric generators
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K17/00—Using steam or condensate extracted or exhausted from steam engine plant
- F01K17/02—Using steam or condensate extracted or exhausted from steam engine plant for heating purposes, e.g. industrial, domestic
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K7/00—Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating
- F01K7/16—Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating the engines being only of turbine type
- F01K7/22—Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating the engines being only of turbine type the turbines having inter-stage steam heating
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste, which comprises a material conveying unit, wherein the material conveying unit is connected with a starting preheating unit, the starting preheating unit is connected with a multistage supercritical water oxidation treatment unit, the multistage supercritical water oxidation treatment unit is connected with a steam turbine generator unit and a starting loop unit, and the steam turbine generator unit is connected with a mixed working medium exhaust steam post-treatment unit. According to the invention, the auxiliary fuel is added to provide active free radicals and reaction heat for supercritical water oxidative decomposition of stubborn pollutants, so that the degradation of refractory pollutants in hazardous waste is promoted in a synergistic manner under relatively mild reaction conditions, the alloy material cost of system equipment is reduced, and the operation safety and reliability are improved.
Description
Technical Field
The invention belongs to the technical field of industrial organic wastewater degradation, and relates to a supercritical water enhanced oxidation treatment coupling power generation system for organic hazardous wastewater.
Background
With the continuous development of industrial production scale and technology in China, the types and discharge amount of industrial wastewater are increasing day by day, and the types and components of the industrial wastewater are more and more complex. The pollution and the harmfulness of organic industrial wastewater such as coal chemical wastewater, pharmaceutical chemical wastewater, printing and dyeing wastewater, pesticide wastewater and the like are the most serious, and high-harmfulness organic compounds can cause cancer and mutation and have great threat to the environment and the human health. In addition, conventional industrial wastewater treatment methods produce large amounts of sludge containing organic hazardous waste. Therefore, efficient, thorough and harmless treatment of hazardous wastes such as refractory industrial organic wastewater, sludge and the like becomes one of the important environmental problems currently faced by China, and the problem is solved properly and is a very arduous and urgent task.
Supercritical Water Oxidation (SCWO) has a wide prospect in the aspect of treating refractory organic pollutants, and can realize efficient and harmless treatment of industrial organic wastewater and sludge. Supercritical water refers to water with temperature and pressure exceeding critical values, in the supercritical water, organic matters, oxygen, nitrogen, carbon dioxide and other gases are mutually soluble in any proportion and can be mutually soluble with the supercritical water, so that an oxidation reaction is carried out under a homogeneous condition, mass transfer resistance is reduced, and reaction rate is improved. Active auxiliary fuel compounds (such as methanol, ethanol, isopropanol and the like) are added into a supercritical water oxidation system, and through active free radicals and reaction heat released by SCWO (auxiliary fuel component) reaction, dynamics and a heat effect are respectively provided for the reaction of stubborn pollutant components, the decomposition of the stubborn pollutant components is synergistically promoted, and further the enhanced degradation of organic pollutants in hazardous waste under relatively mild reaction conditions is realized.
Although the supercritical water oxidation technology has great advantages in the field of organic hazardous waste treatment, the experimental device and the commercialized device for treating the organic hazardous waste by the traditional supercritical water oxidation technology still face the problems to be solved, which are specifically shown in the following aspects:
(1) the recalcitrant components are difficult to completely degrade. In conventional supercritical water oxidation processes, some recalcitrant components are difficult to degrade. Several studies have shown that ammonia is a major intermediate in supercritical water oxidation of nitrogen-containing species and is difficult to degrade. Test results show that the operating temperature of the main reactor needs to reach 700 ℃ to realize efficient degradation of ammonia.
(2) The equipment investment and the operation cost are high. Since the supercritical water oxidation reaction needs to be carried out under high temperature and high pressure, the waste liquid is heated to a subcritical or supercritical state before entering the reactor. At present, most devices preheat materials and the like by preheating hot fluid and electrically heating after reaction, but because a supercritical water oxidation reactor is mainly arranged in a 1-level mode, waste liquid COD is low, efficient heat recovery cannot be realized, and serious electric heating heat compensation is caused in the operation process; the COD concentration of the waste liquid is high, the temperature of the fluid is extremely high due to the oxidation of the waste liquid in the reactor, and although the heat recovery efficiency can be improved, the cost of the main reactor is too high due to the overhigh temperature and the 25MPa operating condition.
Disclosure of Invention
The invention aims to provide a supercritical water enhanced oxidation treatment coupling power generation system for organic hazardous waste, and solves the problems that in the prior art, the stubborn components are difficult to degrade thoroughly, and the operating parameters and the cost are high.
The technical scheme includes that the organic hazardous waste supercritical water enhanced oxidation treatment coupling power generation system comprises a material conveying unit, wherein the material conveying unit is connected with a starting preheating unit, the starting preheating unit is connected with a multistage supercritical water oxidation treatment unit, the multistage supercritical water oxidation treatment unit is connected with a steam turbine generator unit and a starting loop unit, and the steam turbine generator unit is connected with a mixed working medium exhaust steam post-treatment unit.
The present invention is also characterized in that,
the material transport unit comprises an organic wastewater storage tank, a high-pressure material pump, a methanol storage tank and a low-temperature liquid oxygen storage tank, wherein an outlet of the organic wastewater storage tank is connected with the high-pressure material pump, the methanol storage tank is communicated with the high-pressure methanol pump, an outlet of the liquid oxygen storage tank is sequentially connected with the low-temperature liquid oxygen pump, the low-temperature liquid oxygen pump is connected with a liquid oxygen preheating heat exchanger, and the liquid oxygen preheating heat exchanger is connected with a flow regulating valve b and a flow regulating valve c.
The starting preheating unit comprises an air exhaust regenerative heat exchanger, a first preheater, a third heat exchanger and an electric heater, wherein a cold fluid outlet of the air exhaust regenerative heat exchanger is connected with a cold fluid inlet of the first preheater, a cold fluid outlet of the first preheater is connected with a cold fluid inlet of the third preheater, a cold fluid outlet of the third preheater is connected with an inlet of the electric heater, and an outlet of the electric heater is connected with a mixer.
Multistage supercritical water oxidation processing unit includes first-stage supercritical water oxidation reactor, third pre-heater hot-fluid import is connected to first-stage supercritical water oxidation reactor, third pre-heater hot-fluid exit linkage second stage supercritical water oxidation reactor, the hot-fluid import of second pre-heater is connected to second stage supercritical water oxidation reactor, the hot-fluid exit linkage third stage supercritical water oxidation reactor of second pre-heater, first pre-heater hot-fluid import is connected to third stage supercritical water oxidation reactor, first pre-heater hot-fluid export divide into two branch roads, connect electric stop valve c all the way, electric stop valve b is connected to another way.
The steam turbine generator unit comprises a steam turbine high-pressure cylinder, the steam turbine high-pressure cylinder is connected with a second preheater cold fluid inlet, a second preheater cold fluid outlet is connected with a steam turbine intermediate-pressure cylinder, and the steam turbine intermediate-pressure cylinder is connected with a steam turbine low-pressure cylinder.
The starting loop unit comprises an electric stop valve c, the electric stop valve c is connected with a condenser, the condenser is connected with a back pressure valve b, and the back pressure valve b is connected with an organic wastewater storage tank.
The mixed working medium exhaust steam post-processing unit comprises a liquid oxygen preheater, the liquid oxygen preheater is connected with a back pressure valve a, the back pressure valve a is connected with a gas-liquid separator, and the gas-liquid separator is connected with a reclaimed water storage tank.
The high-pressure material pump is connected with the air-extracting heat-returning heat exchanger.
A temperature controller a is arranged at the inlet of the first-stage supercritical water oxidation reactor, and a temperature controller b is arranged at the outlet of the first-stage supercritical water oxidation reactor.
The high-pressure cylinder, the medium-pressure cylinder and the low-pressure cylinder of the steam turbine are all connected with a main shaft of the steam turbine generator, and the main shaft of the steam turbine generator is connected with a generator.
The supercritical water enhanced oxidation treatment coupled power generation system for the organic hazardous waste has the advantages that:
(1) by adding auxiliary fuel into the system, the degradation of refractory organic matters in the hazardous waste can be enhanced under relatively mild reaction conditions;
(2) the oxidant is injected into the reactor in a grading way (three stages), so that the temperature of fluid in the system is accurately controlled, and the operation process parameters of the system are ensured on the premise that the operation temperature in equipment (particularly the reactor) is lower than a safety limit value;
(3) when realizing the innocent treatment of the useless pollutant of danger, coupling steam turbine power generation system, the oxidation of organic matter is exothermic in the high-efficient utilization danger is useless, improves the useless expense of handling of danger.
In conclusion, the supercritical water enhanced oxidation treatment coupling power generation system for the organic hazardous waste can realize the efficient treatment of the refractory pollutants in the hazardous waste, effectively reduce the investment of system equipment and the treatment cost of the hazardous waste and improve the economical efficiency of the system.
Drawings
FIG. 1 is a schematic structural diagram of a supercritical water enhanced oxidation treatment coupled power generation system for hazardous organic waste water.
In the figure, 1, an organic wastewater storage tank, 2, a high-pressure material pump, 3, an air extraction regenerative preheater, 4, a first preheater, 5, a second preheater, 6, a third preheater, 7 electric heaters, 8, a methanol storage tank, 9, a high-pressure methanol pump, 10, a flow regulating valve a, 11, a low-temperature liquid oxygen storage tank, 12, a low-temperature liquid oxygen pump, 13, an electric stop valve a, 14, a flow regulating valve b, 15, a flow regulating valve c, 16, a mixer, 17, a temperature controller a, 18, a first-stage supercritical water oxidation reactor, 19, a temperature controller b, 20, a second-stage supercritical water oxidation reactor, 21, a temperature controller c, 22, a third-stage supercritical water oxidation reactor, 23, a temperature controller d, 24, an electric stop valve b, 25, a pressure controller, 26, a mixed working medium turbine high-pressure cylinder, 27, a mixed working medium turbine intermediate pressure cylinder, 28. the system comprises a mixed working medium turbine low-pressure cylinder, a 29 liquid oxygen preheater, 30 back pressure valves a, 31, a gas-liquid separator, 32 a reclaimed water storage tank, 33 electric stop valves c and 34, a condenser, 35 back pressure valves b and 36, a generator, 37 electric stop valves d and 38 and a turbonator main shaft.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a structure of a supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste, which comprises a material conveying unit, wherein the material conveying unit is connected with a starting preheating unit, the starting preheating unit is connected with a multistage supercritical water oxidation treatment unit, the multistage supercritical water oxidation treatment unit is connected with a steam turbine generator unit and a starting loop unit, and the steam turbine generator unit is connected with a mixed working medium exhaust steam post-treatment unit, as shown in figure 1.
The material conveying unit comprises an organic wastewater storage tank 1, a high-pressure material pump 2, a methanol storage tank 8 and a low-temperature liquid oxygen storage tank 11, wherein the outlet of the organic wastewater storage tank 1 is connected with the high-pressure material pump 2, the methanol storage tank 8 is communicated with a high-pressure methanol pump 9, the outlet of the liquid oxygen storage tank 11 is sequentially connected with a low-temperature liquid oxygen pump 12, the low-temperature liquid oxygen pump 12 is connected with an electric stop valve a13, an electric stop valve a13 is connected with a liquid oxygen preheating heat exchanger 29, and the liquid oxygen preheating heat exchanger 29 is connected with a flow regulating valve b14 and a flow regulating valve;
the starting preheating unit comprises an air extraction regenerative heat exchanger 3, a first preheater 4, a third heat exchanger 6 and an electric heater 7, a high-pressure material pump 2 is connected with the air extraction regenerative heat exchanger 3 through a pipeline, the high-pressure material pump 2 is provided with an electric stop valve d37, a cold fluid outlet of the air extraction regenerative heat exchanger 3 is connected with a cold fluid inlet of the first preheater 4, a cold fluid outlet of the first preheater 4 is connected with a cold fluid inlet of the third preheater 6, a cold fluid outlet of the third preheater 6 is connected with an inlet of the electric heater 7, and an outlet of the electric heater 7 is connected with a mixer 16;
the multi-stage supercritical water oxidation treatment unit comprises a first-stage supercritical water oxidation reactor 18, the first-stage supercritical water oxidation reactor 18 is connected with a hot fluid inlet of a third preheater 6, a hot fluid outlet of the third preheater 6 is connected with a second-stage supercritical water oxidation reactor 20, the second-stage supercritical water oxidation reactor 20 is connected with a hot fluid inlet of a second preheater 5, a hot fluid outlet of the second preheater 5 is connected with a third-stage supercritical water oxidation reactor 22, the third-stage supercritical water oxidation reactor 22 is connected with a hot fluid inlet of a first preheater 4, a hot fluid outlet of the first preheater 4 is divided into two branches, one branch is connected with an electric stop valve c33, and the other branch is connected with an electric stop valve b 24;
the steam turbine generator unit comprises a steam turbine high-pressure cylinder 26, the steam turbine high-pressure cylinder 26 is connected with a cold fluid inlet of the second preheater 5, a cold fluid outlet of the second preheater 5 is connected with a steam turbine intermediate-pressure cylinder 27, the steam turbine intermediate-pressure cylinder 27 is connected with a steam turbine low-pressure cylinder 28, the steam turbine high-pressure cylinder 26, the steam turbine intermediate-pressure cylinder 27 and the steam turbine low-pressure cylinder 28 are all connected with a steam turbine generator main shaft 38, and the steam turbine generator main shaft 38 is connected with a;
the starting loop unit comprises an electric stop valve c33, the electric stop valve c33 is connected with the condenser 34, the condenser 34 is connected with a back pressure valve b35, and the back pressure valve b35 is connected with the organic wastewater storage tank 1;
the mixed working medium exhaust steam post-processing unit comprises a liquid oxygen preheater 29, wherein the liquid oxygen preheater 29 is connected with a back pressure valve a30, the back pressure valve a30 is connected with a gas-liquid separator 31, and the gas-liquid separator 31 is connected with a reclaimed water storage tank 32.
The working principle and the working process of the high-concentration organic industrial wastewater enhanced harmless treatment coupling power generation system are as follows:
and (3) a system starting stage: the electric shutoff valve a13 and the electric shutoff valve b24 are closed, the flow rate adjustment valve a10 is closed, and the electric shutoff valve c33 is opened. Starting the high-pressure material pump 2, inputting the waste liquid in the organic wastewater storage tank 1 into the system through the high-pressure material pump 2, and sequentially passing through the starting preheating unit, the multistage supercritical water oxidation treatment unit and the starting loop unit. The third-stage supercritical water oxidation reactor 22 is connected with the pressure controller 25, and the outlet pressure of the third-stage supercritical water oxidation reactor 22 is gradually increased to 25MPa by adjusting the opening degree of the back pressure valve b 35;
starting an electric heater 7 and a condenser 34, heating the wastewater in the system to 450 ℃ through the electric heater 7, when the temperature at a temperature controller a17 reaches 450 ℃, starting a low-temperature liquid oxygen pump 12, opening an electric stop valve a13, opening a flow control valve b14 and a flow control valve c15, injecting oxygen into the multistage supercritical water oxidation reactor, wherein the temperature at the outlets of the first stage supercritical water oxidation reactor 18 and the second stage supercritical water oxidation reactor 20 is controlled to 600 ℃ by monitoring the temperature controller b19 and the temperature controller c21 respectively and automatically controlling the opening degrees of the flow control valve b14 and the flow control valve c15, and the temperature at the outlets of the first stage supercritical water oxidation reactor 18 and the second stage supercritical water oxidation reactor 20 is controlled by controlling the flow of oxygen, the temperature controller d23 is arranged at the outlet of the first preheater 4, and the temperature controller d23 is connected with the flow control valve a10, the automatic adjustment of the adjusting valve a10 is realized, so that the outlet temperature of the first preheater 4 is controlled at 600 ℃ by controlling the total flow of the methanol; the high-temperature hot fluid from the first stage supercritical water oxidation reactor 18 flows in from the hot fluid inlet of the third preheater 6, flows out from the hot fluid outlet of the third preheater 6 to preheat the organic wastewater, the high-temperature hot fluid from the third stage supercritical water oxidation reactor 22 flows in from the hot fluid inlet of the first preheater 4, and flows out from the hot fluid outlet of the first preheater 4, so as to primarily preheat the organic industrial wastewater, the hot fluid passing through the first preheater in the starting stage passes through the starting circuit unit, the temperature of the fluid is reduced by the condenser 34, and the back pressure valve 35 reduces the pressure to the atmospheric pressure and then flows back to the high-concentration organic wastewater storage tank 1;
and when the temperature measured by the temperature controller d23 is stably kept at 600 ℃, the electric stop valve b24 can be opened, the electric stop valve c33 is closed, and the steam turbine system is connected.
When the system is in normal operation: waste water in an organic waste water storage tank 1 is injected into a system through a high-pressure material pump 2, organic waste liquid enters an electric heater 7 with a temperature controller for supplementary heating after being preliminarily preheated by an air extraction regenerative preheater 3, a first preheater 4 and a third preheater 6, is mixed with auxiliary fuel methanol at a mixer 16, the temperature controller a17 is arranged at the inlet of a first-stage supercritical water oxidation reactor 18, the temperature of a measuring point of the temperature controller a17 is controlled to be 450 ℃ through the electric heater 7, the mixed organic waste water entering the first-stage supercritical water oxidation reactor 18 is mixed with oxygen to generate a supercritical water oxidation reaction, the released heat heats supercritical fluid to 600 ℃, the opening degree of a flow regulating valve b14 is controlled through arranging a temperature controller b19 at the outlet of the first-stage supercritical water oxidation reactor 18, so that the temperature of the supercritical fluid at the outlet is controlled through regulating the oxygen amount entering the first-stage supercritical water oxidation reactor 18, the supercritical fluid heated by the first stage supercritical water oxidation reactor 18 is subjected to heat exchange in the third preheater 6 to be cooled to 450 ℃, and then enters the second stage supercritical water oxidation reactor, the temperature of the outlet supercritical fluid is controlled by adjusting the oxygen amount entering the first stage supercritical water oxidation reactor 20 as same as the first stage supercritical water oxidation reactor 18 and controlling the opening degree of the flow regulating valve c15 through the temperature controller c21 at the outlet, the supercritical fluid heated by the second stage supercritical water oxidation reactor 20 heats the steam from the high pressure cylinder of the steam turbine in the second heat exchanger 5 to achieve the purpose of interstage reheating, the heat fluid from the second heat exchanger 5 enters the third stage supercritical water oxidation reactor, and the organic waste liquid can be subjected to sufficient supercritical oxidation reaction in the third stage supercritical water oxidation reactor to heat the fluid, after the cold materials are preheated by the first preheater 4, the steam parameters of the inlet of the turbine are 600 ℃ and 25MPa, and the control of the inlet temperature of the turbine is realized by controlling the methanol flow of the flow regulating valve a10 by a temperature controller d23 arranged at the outlet of the first preheater 4.
After entering a steam turbine, a mixed working medium with the temperature of 600 ℃ and the pressure of 25MPa sequentially passes through a steam turbine high-pressure cylinder 26, an interstage reheating device, a second preheater 5 and a steam turbine intermediate-pressure cylinder 27, at the outlet of the steam turbine intermediate-pressure cylinder, an air extraction heat regeneration device can extract 40% of steam to preheat cold waste liquid in an air extraction heat regeneration preheater 3, the rest 60% of steam can enter a steam turbine low-pressure cylinder to continue to expand to do work, exhaust steam coming out of the steam turbine low-pressure cylinder is connected with a hot fluid inlet of a liquid oxygen preheater 29, the preheated liquid oxygen is mixed with exhaust steam passing through an air extraction device, and after passing through a back pressure valve 30, a gas-liquid separator 31 is used for2Separating, and allowing the liquid-phase product to flow into a reclaimed water storage tank for reuse.
The invention aims to provide a supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste, which is characterized in that auxiliary fuel is added into the system to provide active free radicals and reaction heat for supercritical water oxidation decomposition of stubborn pollutants, so that enhanced degradation of refractory pollutants in the hazardous waste under relatively mild reaction conditions is promoted in a synergistic manner, the cost of alloy materials of system equipment is reduced, and the operation safety and reliability are improved. The oxidant is injected into the reactor in stages, the accurate control of the temperature of the system fluid is realized by controlling the flow of the oxidants at each stage, and the temperature of the system fluid meets the process operation condition on the premise of ensuring the safety requirement of equipment materials. The supercritical water enhanced oxidation system of the hazardous waste organic substances can generate 25MPa, 600 ℃ mixed working media (comprising H2O, CO2, N2 and the like), the system is coupled with a steam turbine power generation system, the hot fluid preheats the reaction cold materials and the steam turbine interstage reheating after the reaction, the cascade optimal utilization of the energy of the hot fluid after the reaction is realized, the power generation efficiency is improved, and the economic benefit of the system is improved while the hazardous waste pollutants are efficiently treated.
The invention takes methanol as auxiliary fuel for strengthening oxidation, and applies supercritical water strengthening oxidation technology to harmless treatment of refractory industrial wastewater and sludge. Before entering the SCWO reactor, the wastewater and sludge are mixed with auxiliary fuel methanol and undergo a rapid supercritical water oxidation reaction with oxygen in the reactor. In the reaction process, active methanol can be oxidized and decomposed in an early reaction time to release active free radicals and reaction heat at the same time, and the active free radicals can be supplied to react with stubborn pollutants in the system to excite the restrictive decomposition step; meanwhile, the reaction heat released by the methanol reaction can increase the temperature of the reaction system, promote the reaction constant of the auxiliary fuel, accelerate the release of free radicals of the auxiliary fuel and realize the mutual cooperation of the dynamics and the heat effect. Therefore, the auxiliary fuel with a certain concentration is added into the system, so that the degradation of the pollutants difficult to degrade can be enhanced under relatively mild reaction conditions (such as 520 ℃ and 25MPa), the mild reaction conditions not only can greatly reduce the alloy requirements of system equipment and reduce the equipment investment, but also can obviously improve the operation safety of the supercritical water oxidation system. Secondly, the invention adopts an oxidant graded incidence reactor, can realize the accurate control of the reaction temperature in each grade of reactor by adjusting the flow of each grade of oxidant, and simultaneously ensures that the fluid temperature meets the requirements of key process conditions in the system, including the reaction temperature in each grade of reactor and the working medium temperature at the outlet (or the inlet of a steam turbine) of the reactor, on the premise of ensuring that the operation temperature of the reactor is lower than the safety limit value of equipment materials. And finally, in the normal operation stage of the system, under the condition of not adding an external heat source, the parameters of a mixed working medium at the outlet of the SCWO disposal subsystem can reach 25MPa and 600 ℃, a steam turbine power generation system is coupled behind the SCWO subsystem, the energy step optimization utilization of the reacted hot fluid is realized by combining the preheating of a reaction material, the power generation of the steam turbine and the interstage reheating of the steam turbine, the heat of the reacted fluid is efficiently recovered, the disposal cost of the hazardous waste is reduced, and the operation economy of the whole system is improved.
Claims (10)
1. The utility model provides an organic danger is useless supercritical water and is reinforceed oxidation and handle coupling power generation system which characterized in that, includes material transport unit, and material transport unit connects and starts preheating unit, starts preheating unit and connects multistage supercritical water oxidation processing unit, and multistage supercritical water oxidation processing unit connects steam turbine generator unit and start-up loop unit, and steam turbine generator unit connects and mixes working medium exhaust steam after-treatment unit.
2. The supercritical water enhanced oxidation treatment coupling power generation system for organic hazardous waste according to claim 1, wherein the material transportation unit comprises an organic waste water storage tank (1), a high-pressure material pump (2), a methanol storage tank (8) and a low-temperature liquid oxygen storage tank (11), an outlet of the organic waste water storage tank (1) is connected with the high-pressure material pump (2), the methanol storage tank (8) is communicated with the high-pressure methanol pump (9), an outlet of the liquid oxygen storage tank (11) is sequentially connected with the low-temperature liquid oxygen pump (12), the low-temperature liquid oxygen pump (12) is connected with a liquid oxygen preheating heat exchanger (29), and the liquid oxygen preheating heat exchanger (29) is connected with a flow regulating valve b (14) and a flow regulating valve c (15).
3. The supercritical water enhanced oxidation treatment coupled power generation system of organic hazardous waste according to claim 2, wherein the start-up preheating unit comprises an air extraction regenerative heat exchanger (3), a first preheater (4), a third heat exchanger (6) and an electric heater (7), a cold fluid outlet of the air extraction regenerative heat exchanger (3) is connected with a cold fluid inlet of the first preheater (4), a cold fluid outlet of the first preheater (4) is connected with a cold fluid inlet of the third preheater (6), a cold fluid outlet of the third preheater (6) is connected with an inlet of the electric heater (7), and an outlet of the electric heater (7) is connected with the mixer (16).
4. The supercritical water enhanced oxidation treatment coupled power generation system of organic critical waste water of claim 3, wherein the multi-stage supercritical water oxidation treatment unit comprises a first stage supercritical water oxidation reactor (18), the first stage supercritical water oxidation reactor (18) is connected with the hot fluid inlet of a third preheater (6), the hot fluid outlet of the third preheater (6) is connected with a second stage supercritical water oxidation reactor (20), the second stage supercritical water oxidation reactor (20) is connected with the hot fluid inlet of a second preheater (5), the hot fluid outlet of the second preheater (5) is connected with a third stage supercritical water oxidation reactor (22), the third stage supercritical water oxidation reactor (22) is connected with the hot fluid inlet of a first preheater (4), the hot fluid outlet of the first preheater (4) is divided into two branches, one branch is connected with an electric stop valve c (33), the other path is connected with an electric stop valve b (24).
5. The supercritical water enhanced oxidation disposal coupling power generation system of organic hazardous waste according to claim 1, wherein the steam turbine generator unit comprises a steam turbine high-pressure cylinder (26), the steam turbine high-pressure cylinder (26) is connected with a cold fluid inlet of the second preheater (5), a cold fluid outlet of the second preheater (5) is connected with a steam turbine intermediate-pressure cylinder (27), and the steam turbine intermediate-pressure cylinder (27) is connected with a steam turbine low-pressure cylinder (28).
6. The supercritical water enhanced oxidation treatment coupled power generation system of organic hazardous waste according to claim 2, wherein the start loop unit comprises an electric stop valve c (33), the electric stop valve c (33) is connected with a condenser (34), the condenser (34) is connected with a backpressure valve b (35), and the backpressure valve b (35) is connected with the organic waste water storage tank (1).
7. The supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste according to claim 1, wherein the mixed working medium exhaust steam post-treatment unit comprises a liquid oxygen preheater (29), the liquid oxygen preheater (29) is connected with a backpressure valve a (30), the backpressure valve a (30) is connected with a gas-liquid separator (31), and the gas-liquid separator (31) is connected with a reclaimed water storage tank (32).
8. The supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste according to claim 3, characterized in that the high-pressure material pump (2) is connected with the air extraction heat recovery heat exchanger (3).
9. The supercritical water enhanced oxidation treatment coupled power generation system of organic critical waste according to claim 4, wherein a temperature controller a (17) is provided at the inlet of the first stage supercritical water oxidation reactor (18), and a temperature controller b (19) is provided at the outlet of the first stage supercritical water oxidation reactor (18).
10. The supercritical water enhanced oxidation treatment coupled power generation system for organic hazardous waste according to claim 5, wherein the turbine high-pressure cylinder (26), the turbine medium-pressure cylinder (27) and the turbine low-pressure cylinder (28) are all connected with a turbine generator main shaft (38), and the turbine generator main shaft (38) is connected with a generator (36).
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