CN113880224A - Novel supercritical oxidation process - Google Patents
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- 239000007788 liquid Substances 0.000 claims abstract description 137
- 230000001590 oxidative effect Effects 0.000 claims abstract description 55
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a novel supercritical oxidation process, which adopts supercritical oxidation equipment comprising a wastewater pressurizing unit, an oxidation liquid outlet unit, a gas pressurizing unit, a turbine unit, a steam unit, a supercritical oxidation unit and a gas-liquid separation unit, wherein the supercritical oxidation process specifically comprises the following steps: s1: a wastewater pressurization process; s2: a turbine pressurization process; s3: a supercritical oxidation process; s4: circularly switching feeding: circularly switching feeding between the first reaction kettle and the second reaction kettle; s5: heat energy is transferred circularly; s6: gas-liquid separation; s7: the oxidizing liquid outlet unit comprises an oxidizing liquid cooler, the temperature of the liquid is reduced to 50-60 ℃ after passing through the oxidizing liquid cooler, and then the liquid is naturally cooled or air-cooled and discharged; the processing capacity of the supercritical oxidation apparatus was 1m3H is used as the reference value. The invention effectively solves the problem of the oxidation of the industrial wastewater with ultrahigh COD, has high degradation efficiency, can stably run the supercritical oxidation equipment for a long time, and effectively solves the problem of the blockage of the equipment and the pipelineAnd (5) problems are solved.
Description
Technical Field
The invention relates to the technical field of environment-friendly wastewater treatment, in particular to a novel supercritical oxidation process.
Background
The production sewage of chemical industry, electroplating, dye, medicine and other industries generally has the characteristics of high salinity, high COD (chemical oxygen demand) and many toxic and harmful components, and has great harm to the environment and great treatment difficulty. With the increase of the national requirements for environmental protection, the treatment of the sewage becomes extremely urgent.
The supercritical wet oxidation is a novel oxidation technology with high efficiency and wide applicability. Compared with the traditional wet oxidation technology, the supercritical wet oxidation technology is mainly characterized in that the sewage is heated to 374 ℃ or higher and the pressure is 25-40Mpa, so that the water enters a supercritical state. At this time, oxygen is introduced, and almost all organic substances can be completely oxidized into CO2、H2Oxidizing hetero elements such as O, S, P, etc. into corresponding oxyacids, oxidizing halogen elements into corresponding halogen ions, and oxidizing N oxygen elements into N2。
The supercritical oxidation technology effectively overcomes the defect that the traditional wet oxidation dilutes the ultrahigh COD wastewater, simultaneously improves the degradation rate from 45-65% to more than 95%, has short supercritical oxidation reaction time, can be completely oxidized within a few seconds to ten and several seconds, greatly reduces the equipment scale and saves the cost compared with the retention time of wet oxidation for 15-60 min. Compared with other oxidation technologies, the supercritical oxidation method can directly treat the sewage with high COD, high salt and more toxic and harmful components. Compared with incineration and other methods, the supercritical oxidation method has much lower energy consumption, and after wet water oxidation, toxic and harmful substances in the sewage are degraded into low-molecular organic salts, so that secondary pollution to the environment is avoided, and therefore, the supercritical oxidation technology is accepted by many enterprises.
At present, the application of the domestic supercritical wet oxidation is not common, and the main reasons are that: (1) the problem that equipment is easily corroded by sewage in the long-term use process cannot be solved, so that the equipment can only treat sewage without salt or with very low salt generally. (2) The problem of blockage of equipment and pipelines cannot be solved, and the system is difficult to stably operate for a long time.
The applicant redesigns the system to effectively solve the 2 problems, so that the supercritical wet oxidation technology can be applied to engineering practice.
Disclosure of Invention
The invention provides a novel supercritical oxidation process aiming at the defects that the supercritical wet oxidation process in the prior art can only treat waste water without salt or with very low salt, a system is difficult to stably operate for a long time and the like.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a novel supercritical oxidation process adopts supercritical oxidation equipment comprising a wastewater pressurizing unit, an oxidation liquid outlet unit, a gas pressurizing unit, a turbine unit, a steam unit, a supercritical oxidation unit and a gas-liquid separation unit, wherein the supercritical oxidation process specifically comprises the following steps:
s1: a wastewater pressurization process: taking the pretreated industrial wastewater, wherein the COD content in the industrial wastewater is 150000-300000ppm and the total salt content is not higher than 15%, inputting the industrial wastewater into a wastewater pressurizing unit, filtering and pressurizing to 35MPa to form high-pressure wastewater;
s2: a turbine pressurization process: the turbine unit sucks oxygen-enriched gas, the pressure of the oxygen-enriched gas after turbine treatment is increased to 20-25 MPa, the gas is input into the gas pressurizing unit again to be pressurized to obtain high-pressure gas, and then the high-pressure gas and the industrial wastewater are converged to form two-phase fluid and flow into the supercritical oxidation unit;
s3: a supercritical oxidation process: the supercritical oxidation unit comprises a first reaction kettle and a second reaction kettle, wherein a two-phase fluid firstly enters the first reaction kettle, the first reaction kettle is rapidly heated to 280 ℃ and then stops heating, the two-phase fluid starts to be oxidized, the temperature in the first reaction kettle gradually reaches the supercritical temperature along with the oxidation, the two-phase fluid forms an oxidation liquid after being subjected to supercritical oxidation, and a precipitated salt A is crystallized;
s4: circularly switching feeding: continuously feeding and continuously oxidizing in the first reaction kettle, allowing an oxidizing liquid to enter a steam unit, and allowing the steam unit to absorb heat of the oxidizing liquid and transfer the heat back to the first reaction kettle;
when the volume of the precipitated salt A reaches 1/3 of the volume of the first reaction kettle, switching the two-phase fluid into the second reaction kettle, stopping feeding and decompressing the first reaction kettle, discharging the precipitated salt A, and switching the steam unit to supply heat to the second reaction kettle;
when the temperature of the second reaction kettle reaches 280 ℃, the steam unit cuts off heat supply, the two-phase fluid starts to be oxidized, an oxidation liquid is gradually formed, the precipitated salt B is crystallized, and the oxidation liquid enters the steam unit;
when the volume of the precipitated salt B reaches 1/3 of the volume of the second reaction kettle, switching the two-phase fluid into the first reaction kettle, stopping feeding and decompressing the second reaction kettle, discharging the precipitated salt B, switching the steam unit to supply heat to the first reaction kettle, and circularly switching feeding between the first reaction kettle and the second reaction kettle according to the steps;
s5: and (3) heat energy cyclic transfer: the steam unit comprises a steam generator, a softened water inlet end, a steam discharge end and a saturated steam outlet, softened water is taken and enters the steam generator from the softened water inlet end, the softened water is heated by the oxidizing liquid to form steam, the steam is input into the first reaction kettle or the second reaction kettle through the saturated steam outlet, heat energy circulation transfer is formed between the steam generator and the first reaction kettle and between the steam generator and the second reaction kettle, the surplus steam is discharged after being cooled through the steam discharge end, and then the oxidizing liquid continuously flows to the gas-liquid separation unit;
s6: gas-liquid separation: the gas-liquid separation unit separates tail gas and liquid in the oxidation liquid, the tail gas enters a turbine unit, the temperature is firstly reduced to 50-60 ℃, then the pressure of the tail gas is transmitted to oxygen-enriched gas, and the liquid flows into an oxidation liquid water outlet unit;
s7: the oxidizing liquid water outlet unit comprises an oxidizing liquid cooler, and the liquid is cooled to 50-60 ℃ after passing through the oxidizing liquid cooler and then is naturally cooled or air-cooled and discharged;
in step S1, the industrial wastewater is filtered to remove impurities and prevent the wastewater pressurizing unit from being stuck by the impurities. The wastewater pressurizing unit applies pressure to the industrial wastewater to increase the power of the industrial wastewater.
In step S2, the turbine unit can convert the potential energy into the pressure of the oxygen-enriched gas, and the gas pressurizing unit performs secondary pressurization, so that the turbine pressurizing process can significantly save electric energy.
In step S3, the first reaction vessel is preheated to 280 ℃ to reach the subcritical temperature of the two-phase fluid, and as the oxidation proceeds, the temperature in the first reaction vessel continuously rises and reaches the supercritical temperature, so that there is a transition from the subcritical temperature to the supercritical temperature at each feeding.
In step S5, the oxidizing liquid formed by the supercritical oxidation is introduced into the steam unit as a heat source, and the steam generator is introduced with softened water through a softened water inlet port for generating steam. The calorific value generated by the supercritical oxidation is too high, so the calorific value is released by generating steam, and for industrial wastewater with COD content of more than 150000ppm, the heat generated by oxidation is too much, the heat required by the operation of the supercritical oxidation equipment is exceeded, and the surplus steam needs to be discharged through a steam discharge end.
In step S6, the purpose of the exhaust gas cooling is to prevent the turbine from being corroded by the exhaust gas. The turbine unit converts the potential energy of the tail gas into the pressure of the oxygen-rich body, so that the purpose of recycling energy is achieved, and the energy consumption is saved.
Wherein the processing capacity of the supercritical oxidation equipment is 1m3The material of the connecting pipeline of the supercritical oxidation equipment is SS31603 steel, the material of the gas-liquid separation unit is SS31603/Q345R composite plate, and the material of the first reaction kettle and the material of the second reaction kettle are C-276/Q345R explosive composite plates.
The connecting pipeline, the gas-liquid separation unit, the first reaction kettle and the second reaction kettle of the supercritical oxidation equipment are made of the materials, so that the requirement on strength can be met, and the corrosion resistance is high.
Compared with the prior art, the method effectively solves the problem of oxidation of the industrial wastewater with ultrahigh COD (150000-.
Preferably, in the novel supercritical oxidation process, the turbine unit includes a turbine, the gas pressurization unit includes a turbine gas storage tank, an air supercharger and a compressor gas storage tank, the turbine sucks oxygen-enriched gas, pressurizes the oxygen-enriched gas to 25MPa, and stores the oxygen-enriched gas into the turbine gas storage tank, the air supercharger performs secondary pressurization on the oxygen-enriched gas to obtain high-pressure gas, and the pressure of the high-pressure gas is 25-30 MPa and stores the high-pressure gas into the compressor gas storage tank.
The turbine plays the effect of energy reuse, and the air booster compressor plays the effect of secondary pressurization, and turbine gas holder, compressor gas holder play the effect of storage gas.
Preferably, in the novel supercritical oxidation process, the turbine unit further includes a gas cooler, an input end of the gas cooler is connected to the gas-liquid separation unit, and an output end of the gas cooler is connected to the turbine.
The gas cooler is used for cooling the tail gas separated by the gas-liquid separation unit, and the tail gas contains unknown components, so that the purpose of cooling is to prevent the turbine from being corroded by the high-temperature tail gas.
Preferably, in the novel supercritical oxidation process, the pretreatment step of the industrial wastewater is as follows:
a1: taking industrial wastewater to be treated, and determining the content of organic matters containing S element, P element and halogen;
a2: when Xmol of organic matter containing S element, P element and halogen is detected in the industrial wastewater, 2Xmol of NaOH is added for neutralization.
The mixed elements such as S element, P element and the like in the organic matter are oxidized to form corresponding oxyacid, and the halogen element is oxidized to form corresponding halogen ion which can seriously corrode supercritical oxidation equipment, so that the addition of NaOH can play a role in neutralization.
Preferably, in the novel supercritical oxidation process, when the supercritical oxidation reaction is performed in the first reaction kettle and the second reaction kettle, the temperature of the oxidation liquid reaches 380-450 ℃, anchor stirring is adopted, and the stirring speed is set to be 30-45 r/min.
The first reaction kettle and the second reaction kettle have a conversion process from subcritical temperature to supercritical temperature during feeding every time, and the anchor type stirring mode with the stirring speed is adopted, so that gas-liquid mixing can be accelerated, the oxidation speed can be accelerated, and conversion from subcritical temperature to supercritical temperature can be accelerated.
Preferably, in the novel supercritical oxidation process, the first reaction kettle and the second reaction kettle are both provided with a pressure reducing valve and a discharge valve, the supercritical oxidation unit further comprises a control unit, and the pressure reducing valve and the discharge valve are both electrically connected with the control unit.
The first reaction kettle and the second reaction kettle are in a high-pressure environment, so that the pressure is relieved to a normal pressure state through a pressure reducing valve before discharging, and the precipitated salt A or the precipitated salt B is discharged through a discharge valve.
Preferably, in the novel supercritical oxidation process, the first reaction kettle and the second reaction kettle are further provided with drain valves, a steam valve a is arranged between the first reaction kettle and the steam generator, a steam valve B is arranged between the second reaction kettle and the steam generator, the steam valve a, the steam valve B and the drain valves are all electrically connected with the control unit, and the control unit controls the following steps:
b1: when the temperature in the first reaction kettle is lower than 280 ℃, the control unit opens a steam valve A, steam generated by the steam generator heats the first reaction kettle through the steam valve A, and the control unit closes the steam valve A after the steam is heated to 280 ℃;
b2: when the two-phase fluid is switched to enter a second reaction kettle, the control unit opens a steam valve B, steam generated by the steam generator heats the second reaction kettle through the steam valve B until the temperature reaches 280 ℃, the control unit closes the steam valve B, simultaneously the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the first reaction kettle, the first reaction kettle discharges pressure through the pressure reducing valve, condensed water is discharged through the drain valve, and precipitated salt A is discharged gradually through the discharge valve;
b3: when the precipitated salt B in the second reaction kettle reaches 1/3 of the volume of the second reaction kettle, the second reaction kettle is switched back to the first reaction kettle for feeding, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the second reaction kettle, the second reaction kettle discharges pressure through the pressure reducing valve, discharges condensed water through the drain valve and gradually discharges the precipitated salt B through the discharge valve, and meanwhile, the control unit opens a steam valve A to be circularly carried out according to the steps B1-B3.
When 1/3 with excessive salt content is accumulated in the first reaction kettle or the second reaction kettle, the gas content is insufficient, the risk is high, and therefore, the switching of the feeding operation is started when 1/3 with excessive salt content is accumulated. An operator measures the startup time of 1/3 when the salt content of the sediment in the first reaction kettle exceeds the volume, and the control unit automatically switches the feeding by controlling the startup time.
The control unit circularly switches on and off the steam valve A, the steam valve B, the pressure reducing valve, the drain valve and the discharge valve, so that the first reaction kettle and the second reaction kettle are accurately controlled to circularly feed, and the operation efficiency is higher.
Preferably, in the novel supercritical oxidation process, the steam has a temperature of 280 ℃ and a pressure of 10 MPa.
The temperature of 280 ℃ can be reached only when the pressure of the steam reaches more than 8MPa, so that the invention can control the pressure of the steam to be 10MPa and ensure that the temperature of the steam is enough to maintain the reaction temperature in the first reaction kettle or the second reaction kettle.
Preferably, in the novel supercritical oxidation process, the wastewater pressurizing unit comprises a raw water pump, a raw water filter and a high-pressure pump which are sequentially connected, the first reaction kettle and the second reaction kettle are both connected with the high-pressure pump, and the working pressure of the high-pressure pump is 35 MPa.
The working pressure of the high-pressure pump is required to be greater than the pressure in the first reaction kettle and the second reaction kettle, so that the working pressure of the high-pressure pump is set to be 35 MPa. The raw water filter is used for filtering impurities in the industrial wastewater to prevent the impurities from blocking the high-pressure pump.
Preferably, in the novel supercritical oxidation process, the gas cooler, the steam generator and the oxidation liquid cooler are all fixed tube-plate heat exchangers.
The fixed tube-plate heat exchanger has the advantages of simple structure, small manufacturing difficulty and low cost.
Aiming at the defects in the prior art, the invention improves by the following aspects:
1. the industrial wastewater is pretreated (neutralized by adding NAOH), and filtered, so that the corrosion degree of the supercritical oxidation equipment is obviously reduced, the possibility of blockage of the supercritical oxidation equipment is reduced, and the stable operation of the supercritical oxidation equipment is ensured;
2. according to the invention, 2 reaction kettles are used for switching feeding, so that the problem that the 2 reaction kettles are blocked by salt is avoided, and the oxidation liquid is used as a heat source of a steam unit to form heat energy circulation transfer, so that the supercritical oxidation equipment is ensured to operate stably all the time;
3. the invention adopts the combination of the gas-liquid separation unit and the turbine unit to cool the tail gas in the oxidizing liquid, thereby reducing the possibility of corrosion of the turbine, further converting the potential energy of the cooled tail gas into the pressure of oxygen-enriched air to form energy cycle transmission, saving a large amount of energy and ensuring the stable operation of the supercritical oxidation equipment all the time;
4. the COD content of the industrial wastewater is more than 15 ten thousand ppm, a large amount of heat can be released in the supercritical oxidation process, and the operation of equipment needs larger heat, so that the invention utilizes the heat to heat softened water and generate steam, if the heat remains, the heat is converted into the steam to be discharged and can be used by other equipment, thereby ensuring the stable operation of the supercritical oxidation equipment all the time.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the accompanying figure 1 and the detailed description, but they are not intended to limit the invention:
example 1
A novel supercritical oxidation process adopts supercritical oxidation equipment comprising a wastewater pressurizing unit 1, an oxidation liquid outlet unit 2, a gas pressurizing unit 3, a turbine unit 4, a steam unit 5, a supercritical oxidation unit 6 and a gas-liquid separation unit 7, and the supercritical oxidation process specifically comprises the following steps:
s1: a wastewater pressurization process: taking pretreated industrial wastewater, wherein the COD content in the industrial wastewater is 150000ppm, and the total salt content is not higher than 15%, inputting the industrial wastewater into a wastewater pressurizing unit 1, filtering and pressurizing to 35MPa to form high-pressure wastewater;
s2: a turbine pressurization process: the turbine unit 4 sucks oxygen-enriched gas, the pressure of the oxygen-enriched gas after turbine treatment is increased to 20MPa, the gas is input into the gas pressurizing unit 3 again to be pressurized to obtain high-pressure gas, and then the high-pressure gas and the industrial wastewater are converged to form two-phase fluid and flow into the supercritical oxidation unit 6;
s3: a supercritical oxidation process: the supercritical oxidation unit 6 comprises a first reaction kettle 61 and a second reaction kettle 62, wherein two-phase fluid firstly enters the first reaction kettle 61, the first reaction kettle 61 is rapidly heated to 280 ℃ and stops heating, the two-phase fluid starts to be oxidized, the temperature in the first reaction kettle 61 gradually reaches the supercritical temperature along with the oxidation, and the two-phase fluid forms oxidation liquid after being subjected to supercritical oxidation and is crystallized to obtain precipitated salt A;
s4: circularly switching feeding: continuously feeding and continuously oxidizing in the first reaction kettle 61, feeding the oxidizing liquid into a steam unit 5, and absorbing heat of the oxidizing liquid by the steam unit 5 and transferring the heat back to the first reaction kettle 61;
when the volume of the precipitated salt A reaches 1/3 of the volume of the first reaction kettle 61, switching the two-phase fluid into the second reaction kettle 62, stopping feeding and decompressing the first reaction kettle 61, and discharging the precipitated salt A, wherein the steam unit 5 is switched to supply heat to the second reaction kettle 62;
when the temperature of the second reaction kettle 62 reaches 280 ℃, the steam unit 5 cuts off heat supply, the two-phase fluid starts to be oxidized, an oxidation liquid is gradually formed, the precipitated salt B is crystallized, and the oxidation liquid enters the steam unit 5;
when the volume of the precipitated salt B reaches 1/3 of the volume of the second reaction kettle 62, switching the two-phase fluid into the first reaction kettle 61, stopping feeding and decompressing the second reaction kettle 62, and discharging the precipitated salt B, wherein the steam unit 5 is switched to supply heat to the first reaction kettle 61, and feeding is switched between the first reaction kettle 61 and the second reaction kettle 62 in a circulating manner according to the steps;
s5: and (3) heat energy cyclic transfer: the steam unit 5 comprises a steam generator 51, a softened water inlet 52, a steam discharge end 54 and a saturated steam outlet 53, softened water is taken and enters the steam generator 51 from the softened water inlet 52, the softened water is heated by the oxidizing liquid to form steam, the steam is input into the first reaction kettle 61 or the second reaction kettle 62 through the saturated steam outlet 53, heat energy circulation transfer is formed among the steam generator 51, the first reaction kettle 61 and the second reaction kettle 62, the surplus steam is cooled through the steam discharge end 54 and then discharged, and then the oxidizing liquid continues to flow to the gas-liquid separation unit 7;
s6: gas-liquid separation: the gas-liquid separation unit 7 is used for separating tail gas and liquid in the oxidation liquid, the tail gas enters the turbine unit 4, the temperature is firstly reduced to 50 ℃, then the pressure of the tail gas is transmitted to oxygen-enriched gas, and the liquid flows into the oxidation liquid outlet unit 2;
s7: the oxidizing liquid water outlet unit 2 comprises an oxidizing liquid cooler 21, the liquid is cooled to 50 ℃ after passing through the oxidizing liquid cooler 21, and then the liquid is naturally cooled or air-cooled and discharged;
wherein the processing capacity of the supercritical oxidation equipment is 1m3The material of the connecting pipeline of the supercritical oxidation equipment is SS31603 steel, the material of the gas-liquid separation unit 7 is SS31603/Q345R composite plate, and the material of the first reaction kettle 61 and the material of the second reaction kettle 62 are C-276/Q345R explosive composite plates.
Preferably, the turbine unit 4 includes a turbine 41, the gas pressurizing unit 3 includes a turbine gas tank 32, an air supercharger 33, and a compressor gas tank 31, the turbine 41 sucks the oxygen-enriched gas and pressurizes the oxygen-enriched gas to 25MPa to store the oxygen-enriched gas in the turbine gas tank 32, and the air supercharger 33 secondarily pressurizes the oxygen-enriched gas to obtain high-pressure gas, and the high-pressure gas has a pressure of 25MPa and is stored in the compressor gas tank 31.
Preferably, the turbine unit 4 further includes a gas cooler 42, an input end of the gas cooler 42 is connected to the gas-liquid separation unit 7, and an output end of the gas cooler 42 is connected to the turbine 41.
Preferably, the pretreatment steps of the industrial wastewater are as follows:
a1: taking industrial wastewater to be treated, and determining the content of organic matters containing S element, P element and halogen;
a2: when Xmol of organic matter containing S element, P element and halogen is detected in the industrial wastewater, 2Xmol of NaOH is added for neutralization.
Preferably, when the supercritical oxidation reaction is performed in the first reactor 61 and the second reactor 62, the temperature of the oxidation liquid is 380 ℃, the anchor stirring is used, and the stirring speed is 30 r/min.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are both provided with a pressure reducing valve and a discharge valve, and the supercritical oxidation unit 6 further comprises a control unit, wherein the pressure reducing valve and the discharge valve are both electrically connected with the control unit.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are further provided with a steam trap, a steam valve a is provided between the first reaction vessel 61 and the steam generator 51, a steam valve B is provided between the second reaction vessel 62 and the steam generator 51, the steam valve a, the steam valve B and the steam trap are all electrically connected with the control unit, and the control unit controls the following steps:
b1: when the temperature in the first reaction kettle 61 is lower than 280 ℃, the control unit opens a steam valve A, steam generated by the steam generator 51 is used for heating the first reaction kettle 61 through the steam valve A, and the control unit closes the steam valve A after the steam is heated to 280 ℃;
b2: when the two-phase fluid enters the second reaction kettle 62 in a switching mode, the control unit opens a steam valve B, steam generated by the steam generator 51 heats the second reaction kettle 62 through the steam valve B until the temperature reaches 280 ℃, the control unit closes the steam valve B, meanwhile, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the first reaction kettle 61, the first reaction kettle 61 unloads pressure through the pressure reducing valve, discharges condensate water through the drain valve, and gradually discharges precipitated salt A through the discharge valve;
b3: when the precipitated salt B in the second reaction kettle 62 reaches 1/3 of the volume of the second reaction kettle 62, the feeding is switched back to the first reaction kettle 61, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the second reaction kettle 62, the second reaction kettle 62 unloads pressure through the pressure reducing valve, discharges condensed water through the drain valve and gradually discharges the precipitated salt B through the discharge valve, and meanwhile, the control unit opens a steam valve A to cycle according to the steps B1-B3.
Preferably, the steam has a temperature of 280 ℃ and a pressure of 10 MPa.
Preferably, the wastewater pressurizing unit 1 includes a raw water pump 11, a raw water filter 12, and a high-pressure pump 13 connected in sequence, the first reaction vessel 61 and the second reaction vessel 62 are both connected to the high-pressure pump 13, and the working pressure of the high-pressure pump 13 is 35 MPa.
Preferably, the gas cooler 42, the steam generator 51, and the oxidizing liquid cooler 21 are all fixed tube-plate heat exchangers.
Example 2
A novel supercritical oxidation process adopts supercritical oxidation equipment comprising a wastewater pressurizing unit 1, an oxidation liquid outlet unit 2, a gas pressurizing unit 3, a turbine unit 4, a steam unit 5, a supercritical oxidation unit 6 and a gas-liquid separation unit 7, and the supercritical oxidation process specifically comprises the following steps:
s1: a wastewater pressurization process: taking pretreated industrial wastewater, wherein the COD content in the industrial wastewater is 300000ppm, and the total salt content is not higher than 15%, inputting the industrial wastewater into a wastewater pressurizing unit 1, filtering and pressurizing to 35MPa to form high-pressure wastewater;
s2: a turbine pressurization process: the turbine unit 4 sucks oxygen-enriched gas, the pressure of the oxygen-enriched gas after turbine treatment is increased to 25MPa, the gas is input into the gas pressurizing unit 3 again to be pressurized to obtain high-pressure gas, and then the high-pressure gas and the industrial wastewater are converged to form two-phase fluid and flow into the supercritical oxidation unit 6;
s3: a supercritical oxidation process: the supercritical oxidation unit 6 comprises a first reaction kettle 61 and a second reaction kettle 62, wherein two-phase fluid firstly enters the first reaction kettle 61, the first reaction kettle 61 is rapidly heated to 280 ℃ and stops heating, the two-phase fluid starts to be oxidized, the temperature in the first reaction kettle 61 gradually reaches the supercritical temperature along with the oxidation, and the two-phase fluid forms oxidation liquid after being subjected to supercritical oxidation and is crystallized to obtain precipitated salt A;
s4: circularly switching feeding: continuously feeding and continuously oxidizing in the first reaction kettle 61, feeding the oxidizing liquid into a steam unit 5, and absorbing heat of the oxidizing liquid by the steam unit 5 and transferring the heat back to the first reaction kettle 61;
when the volume of the precipitated salt A reaches 1/3 of the volume of the first reaction kettle 61, switching the two-phase fluid into the second reaction kettle 62, stopping feeding and decompressing the first reaction kettle 61, and discharging the precipitated salt A, wherein the steam unit 5 is switched to supply heat to the second reaction kettle 62;
when the temperature of the second reaction kettle 62 reaches 280 ℃, the steam unit 5 cuts off heat supply, the two-phase fluid starts to be oxidized, an oxidation liquid is gradually formed, the precipitated salt B is crystallized, and the oxidation liquid enters the steam unit 5;
when the volume of the precipitated salt B reaches 1/3 of the volume of the second reaction kettle 62, switching the two-phase fluid into the first reaction kettle 61, stopping feeding and decompressing the second reaction kettle 62, and discharging the precipitated salt B, wherein the steam unit 5 is switched to supply heat to the first reaction kettle 61, and feeding is switched between the first reaction kettle 61 and the second reaction kettle 62 in a circulating manner according to the steps;
s5: and (3) heat energy cyclic transfer: the steam unit 5 comprises a steam generator 51, a softened water inlet 52, a steam discharge end 54 and a saturated steam outlet 53, softened water is taken and enters the steam generator 51 from the softened water inlet 52, the softened water is heated by the oxidizing liquid to form steam, the steam is input into the first reaction kettle 61 or the second reaction kettle 62 through the saturated steam outlet 53, heat energy circulation transfer is formed among the steam generator 51, the first reaction kettle 61 and the second reaction kettle 62, the surplus steam is cooled through the steam discharge end 54 and then discharged, and then the oxidizing liquid continues to flow to the gas-liquid separation unit 7;
s6: gas-liquid separation: the gas-liquid separation unit 7 separates tail gas and liquid in the oxidation liquid, the tail gas enters the turbine unit 4, the temperature is firstly reduced to 50-60 ℃, then the pressure of the tail gas is transmitted to oxygen-enriched gas, and the liquid flows into the oxidation liquid outlet unit 2;
s7: the oxidizing liquid water outlet unit 2 comprises an oxidizing liquid cooler 21, the liquid is cooled to 60 ℃ after passing through the oxidizing liquid cooler 21, and then the liquid is naturally cooled or air-cooled and discharged;
wherein the processing capacity of the supercritical oxidation equipment is 1m3The material of the connecting pipeline of the supercritical oxidation equipment is SS31603 steel, the material of the gas-liquid separation unit 7 is SS31603/Q345R composite plate, and the material of the first reaction kettle 61 and the material of the second reaction kettle 62 are C-276/Q345R explosive composite plates.
Preferably, the turbine unit 4 includes a turbine 41, the gas pressurizing unit 3 includes a turbine gas tank 32, an air supercharger 33, and a compressor gas tank 31, the turbine 41 sucks the oxygen-enriched gas, pressurizes the oxygen-enriched gas to 25MPa, and stores the oxygen-enriched gas in the turbine gas tank 32, and the air supercharger 33 secondarily pressurizes the oxygen-enriched gas to obtain a high-pressure gas, and the high-pressure gas has a pressure of 30MPa and is stored in the compressor gas tank 31.
Preferably, the turbine unit 4 further includes a gas cooler 42, an input end of the gas cooler 42 is connected to the gas-liquid separation unit 7, and an output end of the gas cooler 42 is connected to the turbine 41.
Preferably, the pretreatment steps of the industrial wastewater are as follows:
a1: taking industrial wastewater to be treated, and determining the content of organic matters containing S element, P element and halogen;
a2: when Xmol of organic matter containing S element, P element and halogen is detected in the industrial wastewater, 2Xmol of NaOH is added for neutralization.
Preferably, when the supercritical oxidation reaction is performed in the first reactor 61 and the second reactor 62, the temperature of the oxidation liquid is 450 ℃, the anchor stirring is used, and the stirring speed is 45 r/min.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are both provided with a pressure reducing valve and a discharge valve, and the supercritical oxidation unit 6 further comprises a control unit, wherein the pressure reducing valve and the discharge valve are both electrically connected with the control unit.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are further provided with a steam trap, a steam valve a is provided between the first reaction vessel 61 and the steam generator 51, a steam valve B is provided between the second reaction vessel 62 and the steam generator 51, the steam valve a, the steam valve B and the steam trap are all electrically connected with the control unit, and the control unit controls the following steps:
b1: when the temperature in the first reaction kettle 61 is lower than 280 ℃, the control unit opens a steam valve A, steam generated by the steam generator 51 is used for heating the first reaction kettle 61 through the steam valve A, and the control unit closes the steam valve A after the steam is heated to 280 ℃;
b2: when the two-phase fluid enters the second reaction kettle 62 in a switching mode, the control unit opens a steam valve B, steam generated by the steam generator 51 heats the second reaction kettle 62 through the steam valve B until the temperature reaches 280 ℃, the control unit closes the steam valve B, meanwhile, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the first reaction kettle 61, the first reaction kettle 61 unloads pressure through the pressure reducing valve, discharges condensate water through the drain valve, and gradually discharges precipitated salt A through the discharge valve;
b3: when the precipitated salt B in the second reaction kettle 62 reaches 1/3 of the volume of the second reaction kettle 62, the feeding is switched back to the first reaction kettle 61, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the second reaction kettle 62, the second reaction kettle 62 unloads pressure through the pressure reducing valve, discharges condensed water through the drain valve and gradually discharges the precipitated salt B through the discharge valve, and meanwhile, the control unit opens a steam valve A to cycle according to the steps B1-B3.
Preferably, the steam has a temperature of 280 ℃ and a pressure of 10 MPa.
Preferably, the wastewater pressurizing unit 1 includes a raw water pump 11, a raw water filter 12, and a high-pressure pump 13 connected in sequence, the first reaction vessel 61 and the second reaction vessel 62 are both connected to the high-pressure pump 13, and the working pressure of the high-pressure pump 13 is 35 MPa.
Preferably, the gas cooler 42, the steam generator 51, and the oxidizing liquid cooler 21 are all fixed tube-plate heat exchangers.
Example 3
A novel supercritical oxidation process adopts supercritical oxidation equipment comprising a wastewater pressurizing unit 1, an oxidation liquid outlet unit 2, a gas pressurizing unit 3, a turbine unit 4, a steam unit 5, a supercritical oxidation unit 6 and a gas-liquid separation unit 7, and the supercritical oxidation process specifically comprises the following steps:
s1: a wastewater pressurization process: taking pretreated industrial wastewater, wherein the COD content in the industrial wastewater is 200000ppm and the total salt content is not higher than 15%, inputting the industrial wastewater into a wastewater pressurizing unit 1, filtering and pressurizing to 35MPa to form high-pressure wastewater;
s2: a turbine pressurization process: the turbine unit 4 sucks oxygen-enriched gas, the pressure of the oxygen-enriched gas after turbine treatment is increased to 23MPa, the gas is input into the gas pressurizing unit 3 again to be pressurized to obtain high-pressure gas, and then the high-pressure gas and the industrial wastewater are converged to form two-phase fluid and flow into the supercritical oxidation unit 6;
s3: a supercritical oxidation process: the supercritical oxidation unit 6 comprises a first reaction kettle 61 and a second reaction kettle 62, wherein two-phase fluid firstly enters the first reaction kettle 61, the first reaction kettle 61 is rapidly heated to 280 ℃ and stops heating, the two-phase fluid starts to be oxidized, the temperature in the first reaction kettle 61 gradually reaches the supercritical temperature along with the oxidation, and the two-phase fluid forms oxidation liquid after being subjected to supercritical oxidation and is crystallized to obtain precipitated salt A;
s4: circularly switching feeding: continuously feeding and continuously oxidizing in the first reaction kettle 61, feeding the oxidizing liquid into a steam unit 5, and absorbing heat of the oxidizing liquid by the steam unit 5 and transferring the heat back to the first reaction kettle 61;
when the volume of the precipitated salt A reaches 1/3 of the volume of the first reaction kettle 61, switching the two-phase fluid into the second reaction kettle 62, stopping feeding and decompressing the first reaction kettle 61, and discharging the precipitated salt A, wherein the steam unit 5 is switched to supply heat to the second reaction kettle 62;
when the temperature of the second reaction kettle 62 reaches 280 ℃, the steam unit 5 cuts off heat supply, the two-phase fluid starts to be oxidized, an oxidation liquid is gradually formed, the precipitated salt B is crystallized, and the oxidation liquid enters the steam unit 5;
when the volume of the precipitated salt B reaches 1/3 of the volume of the second reaction kettle 62, switching the two-phase fluid into the first reaction kettle 61, stopping feeding and decompressing the second reaction kettle 62, and discharging the precipitated salt B, wherein the steam unit 5 is switched to supply heat to the first reaction kettle 61, and feeding is switched between the first reaction kettle 61 and the second reaction kettle 62 in a circulating manner according to the steps;
s5: and (3) heat energy cyclic transfer: the steam unit 5 comprises a steam generator 51, a softened water inlet 52, a steam discharge end 54 and a saturated steam outlet 53, softened water is taken and enters the steam generator 51 from the softened water inlet 52, the softened water is heated by the oxidizing liquid to form steam, the steam is input into the first reaction kettle 61 or the second reaction kettle 62 through the saturated steam outlet 53, heat energy circulation transfer is formed among the steam generator 51, the first reaction kettle 61 and the second reaction kettle 62, the surplus steam is cooled through the steam discharge end 54 and then discharged, and then the oxidizing liquid continues to flow to the gas-liquid separation unit 7;
s6: gas-liquid separation: the gas-liquid separation unit 7 is used for separating tail gas and liquid in the oxidation liquid, the tail gas enters the turbine unit 4, the temperature is firstly reduced to 55 ℃, then the pressure of the tail gas is transmitted to oxygen-enriched gas, and the liquid flows into the oxidation liquid outlet unit 2;
s7: the oxidizing liquid water outlet unit 2 comprises an oxidizing liquid cooler 21, the liquid is cooled to 55 ℃ after passing through the oxidizing liquid cooler 21, and then the liquid is naturally cooled or air-cooled and discharged;
wherein the processing capacity of the supercritical oxidation equipment is 1m3The material of the connecting pipeline of the supercritical oxidation equipment is SS31603 steel, the material of the gas-liquid separation unit 7 is SS31603/Q345R composite plate, and the material of the first reaction kettle 61 and the material of the second reaction kettle 62 are C-276/Q345R explosive composite plates.
Preferably, the turbine unit 4 includes a turbine 41, the gas pressurizing unit 3 includes a turbine gas tank 32, an air booster 33, and a compressor gas tank 31, the turbine 41 sucks the oxygen-enriched gas and pressurizes the oxygen-enriched gas to 25MPa to store the oxygen-enriched gas in the turbine gas tank 32, and the air booster 33 secondarily pressurizes the oxygen-enriched gas to obtain high-pressure gas having a pressure of 28MPa and stores the high-pressure gas in the compressor gas tank 31.
Preferably, the turbine unit 4 further includes a gas cooler 42, an input end of the gas cooler 42 is connected to the gas-liquid separation unit 7, and an output end of the gas cooler 42 is connected to the turbine 41.
Preferably, the pretreatment steps of the industrial wastewater are as follows:
a1: taking industrial wastewater to be treated, and determining the content of organic matters containing S element, P element and halogen;
a2: when Xmol of organic matter containing S element, P element and halogen is detected in the industrial wastewater, 2Xmol of NaOH is added for neutralization.
Preferably, when the supercritical oxidation reaction is performed in the first reactor 61 and the second reactor 62, the temperature of the oxidation liquid is 400 ℃, the anchor stirring is performed, and the stirring speed is 38 r/min.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are both provided with a pressure reducing valve and a discharge valve, and the supercritical oxidation unit 6 further comprises a control unit, wherein the pressure reducing valve and the discharge valve are both electrically connected with the control unit.
Preferably, the first reaction vessel 61 and the second reaction vessel 62 are further provided with a steam trap, a steam valve a is provided between the first reaction vessel 61 and the steam generator 51, a steam valve B is provided between the second reaction vessel 62 and the steam generator 51, the steam valve a, the steam valve B and the steam trap are all electrically connected with the control unit, and the control unit controls the following steps:
b1: when the temperature in the first reaction kettle 61 is lower than 280 ℃, the control unit opens a steam valve A, steam generated by the steam generator 51 is used for heating the first reaction kettle 61 through the steam valve A, and the control unit closes the steam valve A after the steam is heated to 280 ℃;
b2: when the two-phase fluid enters the second reaction kettle 62 in a switching mode, the control unit opens a steam valve B, steam generated by the steam generator 51 heats the second reaction kettle 62 through the steam valve B until the temperature reaches 280 ℃, the control unit closes the steam valve B, meanwhile, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the first reaction kettle 61, the first reaction kettle 61 unloads pressure through the pressure reducing valve, discharges condensate water through the drain valve, and gradually discharges precipitated salt A through the discharge valve;
b3: when the precipitated salt B in the second reaction kettle 62 reaches 1/3 of the volume of the second reaction kettle 62, the feeding is switched back to the first reaction kettle 61, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the second reaction kettle 62, the second reaction kettle 62 unloads pressure through the pressure reducing valve, discharges condensed water through the drain valve and gradually discharges the precipitated salt B through the discharge valve, and meanwhile, the control unit opens a steam valve A to cycle according to the steps B1-B3.
Preferably, the steam has a temperature of 280 ℃ and a pressure of 10 MPa.
Preferably, the wastewater pressurizing unit 1 includes a raw water pump 11, a raw water filter 12, and a high-pressure pump 13 connected in sequence, the first reaction vessel 61 and the second reaction vessel 62 are both connected to the high-pressure pump 13, and the working pressure of the high-pressure pump 13 is 35 MPa.
Preferably, the gas cooler 42, the steam generator 51, and the oxidizing liquid cooler 21 are all fixed tube-plate heat exchangers.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (10)
1. A novel supercritical oxidation process is characterized in that: the adopted supercritical oxidation equipment comprises a wastewater pressurizing unit (1), an oxidizing liquid water outlet unit (2), a gas pressurizing unit (3), a turbine unit (4), a steam unit (5), a supercritical oxidation unit (6) and a gas-liquid separation unit (7), and the supercritical oxidation process specifically comprises the following steps:
s1: a wastewater pressurization process: taking the pretreated industrial wastewater, wherein the COD content in the industrial wastewater is 150000-300000ppm and the total salt content is not higher than 15%, inputting the industrial wastewater into a wastewater pressurizing unit (1), filtering and pressurizing to 35MPa to form high-pressure wastewater;
s2: a turbine pressurization process: the turbine unit (4) sucks oxygen-enriched gas, the pressure of the oxygen-enriched gas after turbine treatment is increased to 20-25 MPa, the gas is input into the gas pressurizing unit (3) to be pressurized to obtain high-pressure gas, and then the high-pressure gas and the industrial wastewater are converged to form two-phase fluid and flow into the supercritical oxidation unit (6);
s3: a supercritical oxidation process: the supercritical oxidation unit (6) comprises a first reaction kettle (61) and a second reaction kettle (62), wherein a two-phase fluid firstly enters the first reaction kettle (61), the first reaction kettle (61) is rapidly heated to 280 ℃ and then stops heating, the two-phase fluid starts to be oxidized, the temperature in the first reaction kettle (61) gradually reaches the supercritical temperature along with the oxidation, the two-phase fluid forms an oxidation liquid after being subjected to supercritical oxidation, and a precipitated salt A is crystallized;
s4: circularly switching feeding: continuously feeding and continuously oxidizing the oxidizing liquid in the first reaction kettle (61), wherein the oxidizing liquid enters a steam unit (5), and the steam unit (5) absorbs the heat of the oxidizing liquid and transfers the heat back to the first reaction kettle (61);
when the volume of the precipitated salt A reaches 1/3 of the volume of the first reaction kettle (61), switching the two-phase fluid into the second reaction kettle (62), stopping feeding and decompressing the first reaction kettle (61), and discharging the precipitated salt A, wherein the steam unit (5) is switched to supply heat to the second reaction kettle (62);
when the temperature of the second reaction kettle (62) reaches 280 ℃, the steam unit (5) cuts off heat supply, the two-phase fluid starts to be oxidized and gradually forms an oxidizing solution, the precipitated salt B is crystallized, and the oxidizing solution enters the steam unit (5);
when the volume of the precipitated salt B reaches 1/3 of the volume of the second reaction kettle (62), switching the two-phase fluid into the first reaction kettle (61), stopping feeding and decompressing the second reaction kettle (62), discharging the precipitated salt B, switching the steam unit (5) to supply heat to the first reaction kettle (61), and circularly switching feeding between the first reaction kettle (61) and the second reaction kettle (62) according to the steps;
s5: and (3) heat energy cyclic transfer: the steam unit (5) comprises a steam generator (51), a softened water inlet end (52), a steam discharge end (54) and a saturated steam outlet (53), softened water is taken and enters the steam generator (51) from the softened water inlet end (52), the softened water is heated by the oxidizing liquid to form steam, the steam is input into the first reaction kettle (61) or the second reaction kettle (62) through the saturated steam outlet (53), heat energy cyclic transfer is formed among the steam generator (51), the first reaction kettle (61) and the second reaction kettle (62), the surplus steam is cooled through the steam discharge end (54) and then discharged, and then the oxidizing liquid continuously flows to the gas-liquid separation unit (7);
s6: gas-liquid separation: the gas-liquid separation unit (7) separates tail gas and liquid in the oxidation liquid, the tail gas enters the turbine unit (4), the temperature is firstly reduced to 50-60 ℃, then the pressure of the tail gas is transmitted to oxygen-enriched gas, and the liquid flows into the oxidation liquid water outlet unit (2);
s7: the oxidizing liquid water outlet unit (2) comprises an oxidizing liquid cooler (21), and the liquid is cooled to 50-60 ℃ after passing through the oxidizing liquid cooler (21), and then is naturally cooled or air-cooled and discharged;
wherein the processing capacity of the supercritical oxidation equipment is 1m3The material of the connecting pipeline of the supercritical oxidation equipment is SS31603 steel, the material of the gas-liquid separation unit (7) is SS31603/Q345R composite plate, and the material of the first reaction kettle (61) and the material of the second reaction kettle (62) are C-276/Q345R explosive composite plates.
2. The novel supercritical oxidation process according to claim 1, characterized by: turbine unit (4) include turbine (41), and gas pressurization unit (3) include turbine gas holder (32), air booster compressor (33), compressor gas holder (31), turbine (41) inhale oxygen-enriched gas and pressurize to 25MPa, store to in turbine gas holder (32), air booster compressor (33) carry out the secondary pressurization to oxygen-enriched gas, obtain high-pressure gas, high-pressure gas's pressure is 25 ~ 30MPa and stores to in compressor gas holder (31).
3. The novel supercritical oxidation process according to claim 2, characterized in that: the turbine unit (4) further comprises a gas cooler (42), the input end of the gas cooler (42) is connected with the gas-liquid separation unit (7), and the output end of the gas cooler (42) is connected with the turbine (41).
4. The novel supercritical oxidation process according to claim 1, characterized by: the pretreatment steps of the industrial wastewater are as follows:
a1: taking industrial wastewater to be treated, and determining the content of organic matters containing S element, P element and halogen;
a2: when Xmol of organic matter containing S element, P element and halogen is detected in the industrial wastewater, 2Xmol of NaOH is added for neutralization.
5. The novel supercritical oxidation process according to claim 1, characterized by: when the supercritical oxidation reaction is carried out in the first reaction kettle (61) and the second reaction kettle (62), the temperature of the oxidation liquid reaches 380-450 ℃, anchor stirring is adopted, and the stirring speed is set to be 30-45 r/min.
6. The novel supercritical oxidation process according to claim 1, characterized by: all be equipped with relief pressure valve, bleeder valve on first reation kettle (61), second reation kettle (62), supercritical oxidation unit (6) still includes the control unit, relief pressure valve, bleeder valve all with the control unit electricity is connected.
7. The novel supercritical oxidation process according to claim 6, characterized by: still be equipped with the trap on first reation kettle (61), second reation kettle (62), be equipped with steam valve A between first reation kettle (61) and steam generator (51), be equipped with steam valve B between second reation kettle (62) and steam generator (51), steam valve A, steam valve B, trap all with the control unit electricity is connected, the step of the control of control unit is as follows:
b1: when the temperature in the first reaction kettle (61) is lower than 280 ℃, the control unit opens a steam valve A, steam generated by the steam generator (51) is used for heating the first reaction kettle (61) through the steam valve A, and the control unit closes the steam valve A after the steam is heated to 280 ℃;
b2: when the two-phase fluid enters a second reaction kettle (62) in a switching mode, the control unit opens a steam valve B, steam generated by the steam generator (51) heats the second reaction kettle (62) through the steam valve B until the temperature reaches 280 ℃, the control unit closes the steam valve B, meanwhile, the control unit opens a pressure reducing valve, a drain valve and a discharge valve on the first reaction kettle (61), the first reaction kettle (61) discharges pressure through the pressure reducing valve, condensed water is discharged through the drain valve, and precipitated salt A is discharged step by step through the discharge valve;
b3: when the precipitated salt B in the second reaction kettle (62) reaches 1/3 of the volume of the second reaction kettle (62), switching back to the first reaction kettle (61) for feeding, opening a pressure reducing valve, a drain valve and a discharge valve on the second reaction kettle (62) by the control unit, unloading pressure from the second reaction kettle (62) through the pressure reducing valve, discharging condensed water through the drain valve, and gradually discharging the precipitated salt B through the discharge valve, and opening a steam valve A by the control unit at the same time to perform the operation circularly according to the steps B1-B3.
8. The novel supercritical oxidation process according to claim 1, characterized by: the temperature of the steam is 280 ℃ and the pressure is 10 MPa.
9. The novel supercritical oxidation process according to claim 1, characterized by: the waste water pressurizing unit (1) comprises a raw water pump (11), a raw water filter (12) and a high-pressure pump (13) which are sequentially connected, the first reaction kettle (61) and the second reaction kettle (62) are connected with the high-pressure pump (13), and the working pressure of the high-pressure pump (13) is 35 MPa.
10. A novel supercritical oxidation process according to claim 3, characterized in that: the gas cooler (42), the steam generator (51) and the oxidizing liquid cooler (21) are all fixed tube-plate heat exchangers.
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