CN111499072B - Zero emission treatment system and technology for volatile phenol in salt-containing wastewater - Google Patents
Zero emission treatment system and technology for volatile phenol in salt-containing wastewater Download PDFInfo
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- CN111499072B CN111499072B CN202010363900.8A CN202010363900A CN111499072B CN 111499072 B CN111499072 B CN 111499072B CN 202010363900 A CN202010363900 A CN 202010363900A CN 111499072 B CN111499072 B CN 111499072B
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
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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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The invention discloses a zero emission treatment system for volatile phenol in salt-containing wastewater, wherein a second material outlet of a first preheating heat exchanger is communicated with an upper feed inlet of a first supercritical reactor, a first material outlet of a multi-flow heat exchanger is communicated with the upper feed inlet of the second supercritical reactor through a second pipeline, and a medium outlet of the multi-flow heat exchanger is communicated with the lower feed inlet of the first supercritical reactor and the lower feed inlet of the second supercritical reactor. The invention also provides a zero-emission treatment process for the volatile phenol in the salt-containing wastewater. In the invention, an air floatation tank is used for pretreatment, volatile phenol in wastewater is partially removed after pretreatment, and phenol-free wastewater and phenol-containing wastewater are subjected to quality-divided oxidation treatment by utilizing a multi-effect evaporator, so that the phenol-containing water is circularly oxidized in a system without discharge. The micro-discharge of the strong brine end can also achieve that the discharge concentration is not higher than one ten thousandth or one ten thousandth of the inlet water.
Description
Technical Field
The invention relates to the field of treatment of salt-containing phenol-containing wastewater, in particular to a zero-emission treatment system and technology for volatile phenol in salt-containing wastewater.
Background
The high organic matters, high ammonia nitrogen and high toxicity salt-containing phenolic wastewater discharged from chemical plants, pesticide plants and printing and dyeing plants is difficult to treat, and is usually diluted and treated at present. The treatment cost is high, and the treatment is not thorough. Some toxic substances only reach the emission standard after dilution, and are not really converted into harmless substances, and the total amount of the toxic substances is unchanged.
In the prior art, supercritical oxidation technology is mostly adopted for treating high-organic matters, high-ammonia nitrogen and high-toxicity waste salt-containing phenol-containing water, but two bottlenecks are difficult to solve in conventional supercritical treatment, the precipitation of salt in a supercritical state causes reactor blockage, and the size of the reactor, namely the size scale, is limited due to the influence of strong oxidation corrosion at the pressure and the temperature of the reactor.
Disclosure of Invention
The invention aims to provide a zero emission treatment system for volatile phenol in salt-containing wastewater.
The invention also provides a zero-emission treatment process for the volatile phenol in the salt-containing wastewater.
The invention has the innovation points that an air floatation tank is used for pretreatment, volatile phenol in wastewater is partially removed after pretreatment, and the phenol-free wastewater and the phenol-containing wastewater are subjected to quality-divided oxidation treatment by utilizing a multi-effect evaporator, so that the phenol-containing water is circularly oxidized in a system without discharge. The micro-discharge of the strong brine end can also achieve that the discharge concentration is not higher than one ten thousandth or one ten thousandth of the inlet water. In the invention, the upper and lower feed inlets are arranged in the supercritical reactor, the upper water inlet exceeds the supercritical temperature of water, the lower water inlet is the subcritical temperature of water, a temperature gradient is formed up and down, the upper salt is separated out from the water, and the lower subcritical temperature has extremely strong salt solubility, so that the salt is not easy to separate out, and the bottom is not easy to be blocked.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the zero emission treatment system for the volatile phenol in the salt-containing wastewater comprises an air floatation tank, a multi-effect evaporator, a first preheating heat exchanger, a second preheating heat exchanger, a supercritical reactor, a multi-flow heat exchanger, an incineration torch, concentration equipment and a flash tank, wherein the supercritical reactor is provided with a supercritical reactor upper feed inlet and a supercritical reactor lower feed inlet, the supercritical reactor lower feed inlet is positioned at the middle lower part of the side wall of the supercritical reactor, the supercritical reactor is provided with two supercritical reactors, namely the first supercritical reactor and the second supercritical reactor, gas filled into the air floatation tank is inert gas, a gas outlet of the air floatation tank is communicated with the incineration torch, and a water outlet of the air floatation tank is communicated with a material liquid inlet of the multi-effect evaporator through a liquid inlet pipeline; the condensate outlet of the multi-effect evaporator is communicated with the second material inlet of the first preheating heat exchanger through a first pipeline, the oil outlet of the air floatation tank is communicated with the first pipeline, the second material outlet of the first preheating heat exchanger is communicated with the upper feed inlet of the first supercritical reactor, the reaction fluid outlet of the first supercritical reactor is communicated with the medium inlet of the first preheating heat exchanger, the medium outlet of the first preheating heat exchanger is communicated with the feed inlet of the flash tank, the liquid phase discharge port of the flash tank is communicated with the liquid inlet pipeline, and the gas phase discharge port of the flash tank is communicated with the steam inlet of the multi-effect evaporator; the concentrated solution outlet of the concentrating device is communicated with the first material inlet of the second preheating heat exchanger, the first outlet of the second preheating heat exchanger is communicated with the first material inlet of the multi-flow heat exchanger, the first material outlet of the multi-flow heat exchanger is communicated with the upper feed inlet of the second supercritical reactor through a second pipeline, the clear water pipeline is communicated with the second material inlet of the second preheating heat exchanger, the second material outlet of the second preheating heat exchanger is communicated with the second material inlet of the multi-flow heat exchange medium, and the second material outlet of the multi-flow heat exchange medium is communicated with the second pipeline; the salt discharging port of the first supercritical reactor is communicated with the salt discharging port of the second supercritical reactor and then is communicated with the medium inlet of the second preheating heat exchanger, and the medium outlet of the second preheating heat exchanger is communicated with the material heating medium inlet of the concentrating equipment; the reaction fluid outlet of the second supercritical reactor is communicated with the medium inlet of the multi-flow heat exchanger, and the medium outlet of the multi-flow heat exchanger is communicated with the lower feed inlet of the first supercritical reactor and the lower feed inlet of the second supercritical reactor; the concentrating device exhaust port is communicated with the burning torch, the concentrating device heating medium outlet is communicated with the outer exhaust pipeline, and the concentrating device is further provided with a concentrating device steam discharge port.
The reaction fluid outlet of the first supercritical reactor is communicated with the material inlet of the first self-preheating constant temperature pipeline reactor through a third pipeline, and the material outlet of the first self-preheating constant temperature pipeline reactor is communicated with the medium inlet of the first preheating heat exchanger; the reaction fluid outlet of the second supercritical reactor is communicated with the second material inlet of the self-preheating constant temperature pipeline reactor through a fourth pipeline, and the second material outlet of the self-preheating constant temperature pipeline reactor is communicated with the medium inlet of the multi-stream heat exchanger; the liquid inlet pipeline is provided with an oxygen removing device, and the third pipeline and the fourth pipeline are provided with oxygen injecting devices. No oxidation reaction occurs in the supercritical reactor, salt is removed firstly, then the oxidation is carried out in the self-preheating constant temperature pipeline reactor, phenol contained in the wastewater is oxidized, the supercritical reactor is taken as a salt remover, and the self-preheating constant temperature pipeline reactor is taken as an oxidizer. The problems of harsh requirements on materials, insufficient time reaction, incapability of full welding manufacture and the like caused by taking a container as an oxidation reactor are solved, and meanwhile, the risk of blockage of the self-preheating constant temperature pipeline reactor due to salting out in the supercritical oxidation process is also solved.
Further, the self-preheating constant temperature pipeline reactor comprises a reaction pipeline and sealing heads positioned at two ends of the reaction pipeline, two material coils are arranged in the self-preheating constant temperature pipeline reactor and are respectively a first material coil and a second material coil, two ends of the first material coil extend out of the self-preheating constant temperature pipeline reactor and are respectively a first material inlet of the self-preheating constant temperature pipeline reactor and a first material outlet of the self-preheating constant temperature pipeline reactor, two ends of the second material coil extend out of the self-preheating constant temperature pipeline reactor and are respectively a second material inlet of the self-preheating constant temperature pipeline reactor and a second material outlet of the self-preheating constant temperature pipeline reactor, and the self-preheating constant temperature reactor is further provided with a medium inlet of the self-preheating constant temperature reactor and a medium outlet of the self-preheating constant temperature reactor. And compared with a supercritical reactor, the pipeline type structure has fewer welding seams and stronger corrosion resistance.
Further, organic matter dosing devices are further arranged on the third pipeline and the fourth pipeline. Is used for regulating COD.
A zero emission treatment process for volatile phenol in salt-containing wastewater comprises the following steps:
(1) Separating oil, gas and wastewater from the wastewater containing salt and phenol by an air floatation tank, burning the waste gas separated by the air floatation tank by an incineration torch, evaporating the wastewater at the separation part of the air floatation tank by a multi-effect evaporator, heating the waste gas of the multi-effect evaporator by a first preheating heat exchanger, concentrating the concentrated wastewater after multi-effect evaporation by a concentrating device, burning the waste gas generated after concentration by the incineration torch, discharging the concentrated steam, heating the concentrated solution by a second preheating heat exchanger, further heating by a multi-flow heat exchanger, mixing clear water heated by the second preheating heat exchanger and the multi-flow heat exchanger in sequence, and feeding the mixture into an upper feed inlet of the second supercritical reactor after the clear water is mixed to be higher than the supercritical temperature of water; condensed water of the multi-effect evaporator is heated to be higher than the supercritical temperature of water by a first preheating heat exchanger and then enters an upper feed inlet of the first supercritical reactor;
(2) The reaction fluid of the second supercritical reactor is taken as a heating medium and enters a multi-flow heat exchanger for heat exchange, and then enters a lower feed inlet of the first supercritical reactor and a lower feed inlet of the second supercritical reactor respectively after being divided into two flows at the subcritical temperature of water; the reaction fluid of the first supercritical reactor is used for heating the first preheating heat exchanger, the reaction fluid discharged from the first supercritical reactor and the first preheating heat exchanger are subjected to heat exchange and then enter a flash tank for flash evaporation, the gas phase of the flash tank is used for heating a multi-effect evaporator, and the liquid phase of the flash tank and the wastewater separated from the air floatation tank are mixed and enter the multi-effect evaporator for circulation treatment;
(3) The salt-containing wastewater of the first supercritical reactor and the salt-containing wastewater of the second supercritical reactor are mixed and then used for heat exchange of the second preheating heat exchanger, and the salt-containing wastewater and the second preheating heat exchanger are used as a heat source of the concentrating device after heat exchange and then discharged after being used as the heat source.
Further, the liquid phase of the flash tank and the wastewater separated by the air floatation tank in the step (2) are mixed, deoxygenated and then enter a multi-effect evaporator, the reaction fluid of the first supercritical reactor is oxygenated and then enters a self-preheating constant-temperature pipeline reactor for oxidation reaction, the self-preheating constant-temperature pipeline reactor is kept at a constant temperature by adjusting the circulating water quantity, and the reaction fluid of the first supercritical reactor is discharged for heating of the first preheating heat exchanger after oxidation reaction; and (3) oxidizing the reaction fluid of the second supercritical reactor, then, introducing the reaction fluid into a self-preheating constant-temperature pipeline reactor for oxidation reaction, and keeping the constant temperature in the self-preheating constant-temperature pipeline reactor by adjusting the circulating water quantity, and discharging the reaction fluid of the second supercritical reactor for heating of a multi-flow heat exchanger after oxidation reaction. The waste water at the front end of the self-preheating constant temperature pipeline reactor is discharged from the supercritical reactor, so that the flow of the waste water entering the self-preheating constant temperature pipeline reactor is relatively reduced under the condition of meeting the same treatment capacity, the equipment of the self-preheating constant temperature pipeline reactor can be manufactured relatively smaller, the material cost is greatly reduced, the supercritical reactor is used as a salt remover before the waste water enters the supercritical reactor, the oxidation reaction in the supercritical reactor can be avoided, the requirements on the material use of the supercritical reactor can be relaxed, and the oxidation reaction in the self-preheating constant temperature pipeline reactor can be further carried out. The problems of harsh requirements on materials, insufficient time reaction, incapability of full welding manufacture and the like caused by taking a container as an oxidation reactor are solved, and meanwhile, the risk of blockage of the self-preheating constant temperature pipeline reactor due to salting out in the supercritical oxidation process is also solved.
Further, the reaction fluid of the first supercritical reactor and the reaction fluid of the second supercritical reactor enter a self-preheating constant temperature pipeline reactor for reaction after COD is regulated by adding organic matters. Because the oxidation reaction in the self-preheating constant temperature pipeline reactor is exothermic, the reaction heat is enough to maintain the temperature in the self-preheating constant temperature pipeline reactor not to gradually drop and maintain the temperature at about 500 ℃ by adjusting the COD content and matching the oxygen amount of a certain proportion. The circulating water quantity is automatically controlled and regulated, and the surplus heat except heat dissipation is taken away by the softened clean water circulating system.
The beneficial effects of the invention are as follows:
1. in the invention, an air floatation tank is used for pretreatment, volatile phenol in wastewater is partially removed after pretreatment, and phenol-free wastewater and phenol-containing wastewater are subjected to quality-divided oxidation treatment by utilizing a multi-effect evaporator, so that the phenol-containing water is circularly oxidized in a system without discharge. The micro-discharge of the strong brine end can also achieve that the discharge concentration is not higher than one ten thousandth or one ten thousandth of the inlet water.
2. According to the invention, the upper and lower feed inlets are arranged in the supercritical reactor, the upper water inlet exceeds the supercritical temperature of water, the lower water inlet is the subcritical temperature of water, a temperature gradient is formed up and down, the upper salt is separated out from the water, and the lower subcritical temperature has extremely strong salt solubility, so that the salt is not easy to separate out, and the bottom is not easy to be blocked.
3. In the invention, because part of waste water at the front end of the self-preheating constant temperature pipeline reactor is reacted and discharged from the supercritical reactor, under the condition of meeting the same treatment capacity, the flow of waste water entering the self-preheating constant temperature pipeline reactor is relatively reduced, equipment of the self-preheating constant temperature pipeline reactor can be manufactured relatively smaller, the material cost is greatly reduced, the supercritical reactor is firstly deoxidized before entering the supercritical reactor, the oxidation reaction in the supercritical reactor can be avoided, the requirement on the material use of the supercritical reactor can be relaxed, and then the oxidation reaction in the self-preheating constant temperature pipeline reactor can be carried out. The problems of harsh requirements on materials, insufficient time reaction, incapability of full welding manufacture and the like caused by taking a container as an oxidation reactor are solved, and meanwhile, the risk of blockage of the self-preheating constant temperature pipeline reactor due to salting out in the supercritical oxidation process is also solved.
4. The invention separates desalting from oxidation, which greatly reduces the material cost and manufacturing cost of the device, and technically makes the application of supercritical oxidation to large-scale treatment gauge die possible.
5. According to the invention, the salt-containing wastewater of the first supercritical reactor and the second supercritical reactor is phenolic wastewater, the salt content of the water in the first supercritical reactor is small, and the water is used for mixing the salt-containing wastewater of the second supercritical reactor, so that the blockage of a salt discharge pipeline at the second supercritical reactor can be avoided.
6. According to the invention, the phenol-free wastewater is subjected to heat exchange to a subcritical state and flows back to the lower feed inlet of the supercritical reactor, and the salt precipitated in the supercritical reaction is carried out by utilizing the super strong salt solubility under the near supercritical state. Meanwhile, the phenol is effectively isolated between the discharge port and the reaction cavity, so that the phenol discharge is further fundamentally stopped.
7. The whole system fully distributes and utilizes the heat energy.
Drawings
Fig. 1 is a schematic structural diagram of embodiments 1 and 3.
Fig. 2 is a schematic structural diagram of embodiments 2, 4, and 5.
FIG. 3 is a schematic diagram of the structure of a self-preheating isothermal pipeline reactor.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1: as shown in figure 1, the zero emission treatment system for volatile phenol in salt-containing wastewater comprises an air floatation tank 1, a multi-effect evaporator 2, a first preheating heat exchanger 3, a second preheating heat exchanger 4, a supercritical reactor, a multi-flow heat exchanger 6, an incineration torch 7, concentration equipment 8 and a flash tank 9, wherein the supercritical reactor is provided with an upper feed inlet of the supercritical reactor and a lower feed inlet of the supercritical reactor, the lower feed inlet of the supercritical reactor is positioned at the middle lower part of the side wall of the supercritical reactor, the supercritical reactor is provided with two supercritical reactors 5-1 and 5-2 respectively, gas filled into the air floatation tank 1 is inert gas, a gas outlet 1.1 of the air floatation tank is communicated with the incineration torch 7, and a water outlet 1.2 of the air floatation tank is communicated with a feed liquid inlet 2.1 of the multi-effect evaporator through a liquid inlet pipeline 10; the condensate outlet 2.4 of the multi-effect evaporator is communicated with the material inlet 3.1 of the first preheating heat exchanger, the condensate outlet 2.4 of the multi-effect evaporator is communicated with the material inlet 3.3 of the second preheating heat exchanger through a first pipeline 11, the oil outlet 1.3 of the air floatation tank is communicated with the first pipeline 11, the material outlet 3.4 of the first preheating heat exchanger is communicated with the upper feed inlet 5-1.1 of the first supercritical reactor, the reaction fluid outlet 5-1.2 of the first supercritical reactor is communicated with the medium inlet 3.5 of the first preheating heat exchanger, the medium outlet 3.6 of the first preheating heat exchanger is communicated with the feed inlet 9.1 of the flash tank, the liquid outlet 9.2 of the flash tank is communicated with the liquid inlet pipeline 10, and the gas outlet 9.3 of the flash tank is communicated with the steam inlet 2.5 of the multi-effect evaporator; the concentrated solution outlet 8.2 of the concentrating device is communicated with the first material inlet 4.1 of the second preheating heat exchanger, the first outlet 4.2 of the second preheating heat exchanger is communicated with the first material inlet 6.1 of the multi-stream heat exchanger, the first material outlet 6.2 of the multi-stream heat exchanger is communicated with the upper material inlet 5-2.1 of the second supercritical reactor through a second pipeline 12, the clear water pipeline 13 is communicated with the second material inlet 4.3 of the second preheating heat exchanger, the second material outlet 4.4 of the second preheating heat exchanger is communicated with the second material inlet 6.3 of the multi-stream heat exchange medium, and the second material outlet 6.3 of the multi-stream heat exchange medium is communicated with the second pipeline 12; the salt discharging port of the first supercritical reactor is 5-1.3, the salt discharging port of the second supercritical reactor is 5-2.3 communicated with the medium inlet 4.5 of the second preheating heat exchanger, and the medium outlet 4.6 of the second preheating heat exchanger is communicated with the material heating medium inlet 8.3 of the concentration equipment; the reaction fluid outlet 5-2.2 of the second supercritical reactor is communicated with the medium inlet 6.5 of the multi-flow heat exchanger, and the medium outlet 6.6 of the multi-flow heat exchanger is communicated with the lower feed inlet 5-1.4 of the first supercritical reactor and the lower feed inlet 5-2.4 of the second supercritical reactor; the concentrating device exhaust port 8.4 is communicated with the burning torch 7, the concentrating device heating medium outlet 8.5 is communicated with the outer exhaust pipeline 14, and the concentrating device 8 is also provided with a concentrating device steam discharge port 8.6.
Example 2: as shown in figure 2, the zero emission treatment system for volatile phenol in salt-containing wastewater comprises an air floatation tank 1, a multi-effect evaporator 2, a first preheating heat exchanger 3, a second preheating heat exchanger 4, a supercritical reactor 5, a multi-flow heat exchanger 6, an incineration torch 7, concentration equipment 8 and a flash tank 9, wherein the supercritical reactor 5 is provided with a supercritical reactor upper feed inlet and a supercritical reactor lower feed inlet, the supercritical reactor lower feed inlet is positioned at the middle lower part of the side wall of the supercritical reactor 5, the supercritical reactor 5 is provided with two supercritical reactors 5-1 and 5-2 respectively, the air floatation tank gas outlet 1.1 is communicated with the incineration torch 7, and the air floatation tank water outlet 1.2 is communicated with a multi-effect evaporator feed liquid inlet 2.1 through a liquid inlet pipeline 10; the condensate outlet 2.4 of the multi-effect evaporator is communicated with the material inlet 3.1 of the first preheating heat exchanger, the condensate outlet 2.4 of the multi-effect evaporator is communicated with the material inlet 3.3 of the second preheating heat exchanger through the first pipeline 11, the oil outlet 1.3 of the air flotation tank is communicated with the first pipeline 11, the material outlet 3.4 of the first preheating heat exchanger is communicated with the upper feed inlet 5-1.1 of the first supercritical reactor, the first supercritical reactor 5-1 and the second supercritical reactor 5-2 are respectively provided with a self-preheating constant temperature pipeline reactor 15, the self-preheating constant temperature pipeline reactor 15 comprises a reaction pipeline 15.6 and a sealing head 15.7 positioned at two ends of the reaction pipeline 15.6, two material coils 15.8 and 15.9 of the second material coil are respectively arranged in the self-preheating constant temperature pipeline reactor 15, the first constant temperature pipeline 15.8 and the second constant temperature pipeline 15.8 extend out of the self-preheating pipeline 15 and the constant temperature pipeline 15.9 of the self-preheating pipeline 15, and the two constant temperature pipeline 15.10 of the self-preheating constant temperature pipeline 15.6 are respectively arranged at the two ends of the self-preheating constant temperature pipeline 15 and the two ends of the self-preheating pipeline 15, and the medium inlet 15.10 of the self-preheating pipeline 15 is also provided with a constant temperature pipeline 15.10 and a constant temperature pipeline 15, and a constant temperature medium outlet 15 is respectively arranged at the two ends of the self-preheating constant temperature pipeline 15, and a constant temperature 15 is respectively, the two material inlet 15 is a constant temperature 15 is arranged at the self-temperature constant temperature and a constant temperature 15, and a constant temperature 15 is a constant temperature 15, a constant temperature and a constant temperature 15. The reaction fluid outlet 5-1.2 of the first supercritical reactor is communicated with the material inlet 15.1 of the first self-preheating constant temperature pipeline reactor through a third pipeline 16, and the material outlet 15.2 of the first self-preheating constant temperature pipeline reactor is communicated with the medium inlet 3.5 of the first preheating heat exchanger; the medium outlet 3.6 of the first preheating heat exchanger is communicated with the feeding port 9.1 of the flash tank, the liquid phase discharging port 9.2 of the flash tank is communicated with the liquid inlet pipeline 10, and the gas phase discharging port 9.3 of the flash tank is communicated with the steam inlet 2.5 of the multi-effect evaporator; the concentrated solution outlet 8.2 of the concentrating device is communicated with the first material inlet 4.1 of the second preheating heat exchanger, the first outlet 4.2 of the second preheating heat exchanger is communicated with the first material inlet 6.1 of the multi-stream heat exchanger, the first material outlet 6.2 of the multi-stream heat exchanger is communicated with the upper material inlet 5-2.1 of the second supercritical reactor through a second pipeline 12, the clear water pipeline 13 is communicated with the second material inlet 4.3 of the second preheating heat exchanger, the second material outlet 4.4 of the second preheating heat exchanger is communicated with the second material inlet 6.3 of the multi-stream heat exchange medium, and the second material outlet 6.4 of the multi-stream heat exchange medium is communicated with the second pipeline 12; the salt discharging port of the first supercritical reactor is 5-1.3, the salt discharging port of the second supercritical reactor is 5-2.3 communicated with the medium inlet 4.5 of the second preheating heat exchanger, and the medium outlet 4.6 of the second preheating heat exchanger is communicated with the material heating medium inlet 8.3 of the concentration equipment; the reaction fluid outlet 5-2.2 of the second supercritical reactor is communicated with the second material inlet 15.3 of the self-preheating constant temperature pipeline reactor through a fourth pipeline 17, and the second material outlet 15.4 of the self-preheating constant temperature pipeline reactor is communicated with the medium inlets 6.5 of the multi-flow heat exchangers; the liquid inlet pipeline 10 is provided with an oxygen removing device 18, the third pipeline 16 and the fourth pipeline 17 are provided with an oxygen injecting device 19, and the third pipeline 16 and the fourth pipeline 17 are also provided with an organic matter dosing device 20. The medium outlet 6.6 of the multi-flow heat exchanger is communicated with the lower feed inlet 5-1.4 of the first supercritical reactor and the lower feed inlet 5-2.4 of the second supercritical reactor; the concentrating device exhaust port 8.4 is communicated with the burning torch 7, the concentrating device heating medium outlet 8.5 is communicated with the outer exhaust pipeline 14, and the concentrating device 8 is also provided with a concentrating device steam discharge port 8.6.
Example 3: as shown in fig. 1, a zero emission treatment process for volatile phenol in salt-containing wastewater comprises the following steps: separating oil, gas and wastewater from the wastewater containing salt and phenol by an air floatation tank 1, burning the waste gas separated by the air floatation tank 1 by an burning torch 7, evaporating the waste water separated by the air floatation tank 1 by a multi-effect evaporator 2, burning the waste gas of the multi-effect evaporator 2 by the burning torch 7, heating the concentrated waste water after multi-effect evaporation by a first preheating heat exchanger 3, concentrating the waste gas generated after concentration by a concentrating device 8, burning the burning torch 7, discharging the concentrated steam, heating the concentrated concentrate by a second preheating heat exchanger 4, further heating by a plurality of heat exchangers 6, mixing the concentrated concentrate with clear water heated by the second preheating heat exchanger 4 and the plurality of heat exchangers 6 in sequence, and feeding the mixture into an upper feed inlet 5-2.1 of the second supercritical reactor after the clear water is heated to be higher than the supercritical temperature of water; the condensed water of the multi-effect evaporator 2 is heated to be higher than the supercritical temperature of water by a first preheating heat exchanger 3 and then enters into a feed inlet 5-1.1 at the upper part of the first supercritical reactor; the reaction fluid of the second supercritical reactor 5-2 is used as a heating medium and enters a multi-flow heat exchanger for heat exchange to the subcritical temperature of water, and then is divided into two flows which respectively enter a lower feed inlet 5-1.4 of the first supercritical reactor and a lower feed inlet 5-2.4 of the second supercritical reactor; the reaction fluid of the first supercritical reactor 5-1 is used for heating the first preheating heat exchanger 3, the reaction fluid discharged from the first supercritical reactor 5-1 and the first preheating heat exchanger 3 are subjected to heat exchange and then enter a flash tank 9 for flash evaporation, the gas phase of the flash tank 9 is used for heating the multi-effect evaporator 2, and the liquid phase of the flash tank 9 and the wastewater separated from the air floatation tank 1 are mixed and enter the multi-effect evaporator 2 for circulation treatment; the salt-containing wastewater of the first supercritical reactor 5-1 and the second supercritical reactor 5-2 are mixed and then used for heat exchange of the second preheating heat exchanger 4, and the salt-containing wastewater and the second preheating heat exchanger 4 are used as a heat source of the concentration device 8 after heat exchange and are discharged after being used as a heat source.
Example 4: as shown in fig. 2, a zero emission treatment process for volatile phenol in salt-containing wastewater comprises the following steps: separating oil, gas and wastewater from the wastewater containing salt and phenol by an air floatation tank 1, burning the waste gas separated by the air floatation tank 1 by an burning torch 7, evaporating the waste water separated by the air floatation tank 1 by a multi-effect evaporator 2, burning the waste gas of the multi-effect evaporator 2 by the burning torch 7, heating the concentrated waste water after multi-effect evaporation by a first preheating heat exchanger 3, concentrating the waste gas generated after concentration by a concentrating device 8, burning the burning torch 7, discharging the concentrated steam, heating the concentrated concentrate by a second preheating heat exchanger 4, further heating by a plurality of heat exchangers 6, mixing the concentrated concentrate with clear water heated by the second preheating heat exchanger 4 and the plurality of heat exchangers 6 in sequence, and feeding the mixture into an upper feed inlet 5-2.1 of the second supercritical reactor after the clear water is heated to be higher than the supercritical temperature of water; the condensed water of the multi-effect evaporator 2 is heated to be higher than the supercritical temperature of water by a first preheating heat exchanger 3 and then enters into a feed inlet 5-1.1 at the upper part of the first supercritical reactor; the liquid phase of the flash tank 9 and the wastewater separated by the air floatation tank 1 are mixed and then are deoxidized and enter the multi-effect evaporator 2, then the reaction fluid of the No. two supercritical reactors 5-2 is oxygenated and COD is regulated and then enters the self-preheating constant temperature pipeline reactor 15 for oxidation reaction, the self-preheating constant temperature pipeline reactor 15 keeps constant temperature by regulating the circulating water quantity, the reaction fluid of the No. two supercritical reactors 5-2 is discharged after oxidation reaction and is used for heating the multi-strand heat exchanger 6 and is subjected to heat exchange with the multi-strand heat exchanger 6 until the temperature is the subcritical temperature of water, and two flows respectively enter the lower feed inlet 5-1.4 of the No. one supercritical reactor and the lower feed inlet 5-2.4 of the No. two supercritical reactors; the reaction fluid of the first supercritical reactor 5-1 is oxidized and COD is regulated, then enters a self-preheating constant temperature pipeline 15 reactor for oxidation reaction, the self-preheating constant temperature pipeline reactor 15 keeps constant temperature by regulating the circulating water quantity, and the reaction fluid of the first supercritical reactor 5-1 is discharged for heating of the first preheating heat exchanger 3 after oxidation reaction; the reaction fluid discharged from the first supercritical reactor 5-1 exchanges heat with the first preheating heat exchanger 3, and then enters a flash tank 9 for flash evaporation, the gas phase of the flash tank 9 is used for heating the multi-effect evaporator 2, and the liquid phase of the flash tank 9 and the wastewater separated from the air floatation tank 1 are mixed and enter the multi-effect evaporator 2 for circular treatment; the salt-containing wastewater of the first supercritical reactor 5-1 and the second supercritical reactor 5-2 are mixed and then used for heat exchange of the second preheating heat exchanger 4, and the salt-containing wastewater and the second preheating heat exchanger 4 are used as a heat source of the concentration device 8 after heat exchange and are discharged after being used as a heat source.
Example 5: as shown in fig. 2, a zero emission treatment process for volatile phenol in salt-containing wastewater comprises the following steps: separating oil, gas and wastewater from the wastewater containing salt and phenol by using an air floatation tank 1, burning the waste gas separated by the air floatation tank 1 by using an burning torch 7, evaporating the waste water separated by the air floatation tank 1 by using a multi-effect evaporator 2, burning the waste gas of the multi-effect evaporator 2 by using the burning torch 7, heating the concentrated waste water after multi-effect evaporation by using a first preheating heat exchanger 3, concentrating the waste gas generated after concentration by using a concentrating device 8, burning the burning torch 7, discharging the concentrated steam, heating the concentrated concentrate by using a second preheating heat exchanger 4, further heating by using a plurality of heat exchangers 6, and mixing the concentrated concentrate with clear water heated by the second preheating heat exchanger 4 and the plurality of heat exchangers 6 in sequence until the clear water is mixed to 390 ℃ and enters an upper feed inlet 5-2.1 of the second supercritical reactor; condensed water of the multi-effect evaporator 2 is heated to 390 ℃ by a first preheating heat exchanger 3 and enters an upper feed inlet 5-1.1 of a first supercritical reactor; the liquid phase of the flash tank 9 and the wastewater separated by the air floatation tank 1 are mixed and then are deoxidized and enter the multi-effect evaporator 2, then the reaction fluid of the No. two supercritical reactors 5-2 is oxygenated and COD is regulated and then enters the self-preheating constant temperature pipeline reactor 15 for oxidation reaction, the temperature in the self-preheating constant temperature pipeline reactor 15 is kept at 500 ℃ by regulating the circulating water quantity in the self-preheating constant temperature pipeline reactor 15, the reaction fluid of the No. two supercritical reactors 5-2 is discharged after oxidation reaction and used for heating the multi-strand heat exchanger 6 and is subjected to heat exchange with the multi-strand heat exchanger 6 and then enters the lower feed inlet 5-1.4 of the No. one supercritical reactor and the lower feed inlet 5-2.4 of the No. two supercritical reactors respectively after the temperature is 365 ℃; the reaction fluid of the first supercritical reactor 5-1 is oxidized and COD is regulated, then enters a self-preheating constant temperature pipeline 15 reactor for oxidation reaction, the self-preheating constant temperature pipeline reactor 15 keeps constant temperature by regulating the circulating water quantity, and the reaction fluid of the first supercritical reactor 5-1 is discharged for heating of the first preheating heat exchanger 3 after oxidation reaction; the reaction fluid discharged from the first supercritical reactor 5-1 exchanges heat with the first preheating heat exchanger 3, and then enters a flash tank 9 for flash evaporation, the gas phase of the flash tank 9 is used for heating the multi-effect evaporator 2, and the liquid phase of the flash tank 9 and the wastewater separated from the air floatation tank 1 are mixed and enter the multi-effect evaporator 2 for circular treatment; the salt-containing wastewater of the first supercritical reactor 5-1 and the second supercritical reactor 5-2 are mixed and then used for heat exchange of the second preheating heat exchanger 4, and the salt-containing wastewater and the second preheating heat exchanger 4 are used as a heat source of the concentration device 8 after heat exchange and are discharged after being used as a heat source.
The described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (7)
1. The zero emission treatment system for the volatile phenol in the salt-containing wastewater is characterized by comprising an air floatation tank, a multi-effect evaporator, a first preheating heat exchanger, a second preheating heat exchanger, a supercritical reactor, a multi-flow heat exchanger, an incineration torch, concentrating equipment and a flash tank, wherein the supercritical reactor is provided with a supercritical reactor upper feed inlet and a supercritical reactor lower feed inlet, the supercritical reactor lower feed inlet is positioned at the middle lower part of the side wall of the supercritical reactor, the supercritical reactor is provided with two supercritical reactors, namely the first supercritical reactor and the second supercritical reactor, gas filled into the air floatation tank is inert gas, a gas outlet of the air floatation tank is communicated with the incineration torch, and a water outlet of the air floatation tank is communicated with a material liquid inlet of the multi-effect evaporator through a liquid inlet pipeline; the condensate outlet of the multi-effect evaporator is communicated with the second material inlet of the first preheating heat exchanger through a first pipeline, the oil outlet of the air floatation tank is communicated with the first pipeline, the second material outlet of the first preheating heat exchanger is communicated with the upper feed inlet of the first supercritical reactor, the reaction fluid outlet of the first supercritical reactor is communicated with the medium inlet of the first preheating heat exchanger, the medium outlet of the first preheating heat exchanger is communicated with the feed inlet of the flash tank, the liquid phase discharge port of the flash tank is communicated with the liquid inlet pipeline, and the gas phase discharge port of the flash tank is communicated with the steam inlet of the multi-effect evaporator; the concentrated solution outlet of the concentrating device is communicated with the first material inlet of the second preheating heat exchanger, the first outlet of the second preheating heat exchanger is communicated with the first material inlet of the multi-flow heat exchanger, the first material outlet of the multi-flow heat exchanger is communicated with the upper feed inlet of the second supercritical reactor through a second pipeline, the clear water pipeline is communicated with the second material inlet of the second preheating heat exchanger, the second material outlet of the second preheating heat exchanger is communicated with the second material inlet of the multi-flow heat exchange medium, and the second material outlet of the multi-flow heat exchange medium is communicated with the second pipeline; the salt discharging port of the first supercritical reactor is communicated with the salt discharging port of the second supercritical reactor and then is communicated with the medium inlet of the second preheating heat exchanger, and the medium outlet of the second preheating heat exchanger is communicated with the material heating medium inlet of the concentrating equipment; the reaction fluid outlet of the second supercritical reactor is communicated with the medium inlet of the multi-flow heat exchanger, and the medium outlet of the multi-flow heat exchanger is communicated with the lower feed inlet of the first supercritical reactor and the lower feed inlet of the second supercritical reactor; the concentrating device exhaust port is communicated with the burning torch, the concentrating device heating medium outlet is communicated with the outer exhaust pipeline, and the concentrating device is further provided with a concentrating device steam discharge port.
2. The zero emission treatment system for volatile phenol in salt-containing wastewater according to claim 1, wherein the rear ends of the first supercritical reactor and the second supercritical reactor are respectively provided with a self-preheating constant temperature pipeline reactor, a reaction fluid outlet of the first supercritical reactor is communicated with a first material inlet of the self-preheating constant temperature pipeline reactor through a third pipeline, and a first material outlet of the self-preheating constant temperature pipeline reactor is communicated with a first preheating heat exchanger medium inlet; the reaction fluid outlet of the second supercritical reactor is communicated with the second material inlet of the self-preheating constant temperature pipeline reactor through a fourth pipeline, and the second material outlet of the self-preheating constant temperature pipeline reactor is communicated with the medium inlet of the multi-stream heat exchanger; the liquid inlet pipeline is provided with an oxygen removing device, and the third pipeline and the fourth pipeline are provided with oxygen injecting devices.
3. The zero-emission treatment system for volatile phenol in salt-containing wastewater according to claim 2, wherein the self-preheating constant temperature pipeline reactor comprises a reaction pipeline and sealing heads positioned at two ends of the reaction pipeline, two material coils are respectively a first material coil and a second material coil in the self-preheating constant temperature pipeline reactor, two ends of the first material coil extend out of the self-preheating constant temperature pipeline reactor and a first material inlet and a first material outlet of the self-preheating constant temperature pipeline reactor respectively, two ends of the second material coil extend out of the self-preheating constant temperature pipeline reactor and a second material inlet and a second material outlet of the self-preheating constant temperature pipeline reactor respectively, and a medium inlet and a medium outlet of the self-preheating constant temperature reactor are further arranged on the self-preheating constant temperature reactor.
4. The zero release treatment system for volatile phenol in saline wastewater of claim 2, wherein the third pipeline and the fourth pipeline are further provided with organic chemical adding devices.
5. A zero-emission treatment process for volatile phenol in salt-containing wastewater is characterized by comprising the following steps of:
(1) Separating oil, gas and wastewater from the wastewater containing salt and phenol by an air floatation tank, burning the waste gas separated by the air floatation tank by an incineration torch, evaporating the wastewater at the separation part of the air floatation tank by a multi-effect evaporator, heating the waste gas of the multi-effect evaporator by a first preheating heat exchanger, concentrating the concentrated wastewater after multi-effect evaporation by a concentrating device, burning the waste gas generated after concentration by the incineration torch, discharging the concentrated steam, heating the concentrated solution by a second preheating heat exchanger, further heating by a multi-flow heat exchanger, mixing clear water heated by the second preheating heat exchanger and the multi-flow heat exchanger in sequence, and feeding the mixture into an upper feed inlet of the second supercritical reactor after the clear water is mixed to be higher than the supercritical temperature of water; condensed water of the multi-effect evaporator is heated to be higher than the supercritical temperature of water by a first preheating heat exchanger and then enters an upper feed inlet of the first supercritical reactor;
(2) The reaction fluid of the second supercritical reactor is taken as a heating medium and enters a multi-flow heat exchanger for heat exchange, and then enters a lower feed inlet of the first supercritical reactor and a lower feed inlet of the second supercritical reactor respectively after being divided into two flows at the subcritical temperature of water; the reaction fluid of the first supercritical reactor is used for heating the first preheating heat exchanger, the reaction fluid discharged from the first supercritical reactor and the first preheating heat exchanger are subjected to heat exchange and then enter a flash tank for flash evaporation, the gas phase of the flash tank is used for heating a multi-effect evaporator, and the liquid phase of the flash tank and the wastewater separated from the air floatation tank are mixed and enter the multi-effect evaporator for circulation treatment;
(3) The salt-containing wastewater of the first supercritical reactor and the salt-containing wastewater of the second supercritical reactor are mixed and then used for heat exchange of the second preheating heat exchanger, and the salt-containing wastewater and the second preheating heat exchanger are used as a heat source of the concentrating device after heat exchange and then discharged after being used as the heat source.
6. The zero-emission treatment process for volatile phenol in salt-containing wastewater according to claim 5, wherein the liquid phase of the flash tank and the wastewater separated by the air floatation tank in the step (2) are mixed, deoxygenated and then enter a multi-effect evaporator, the reaction fluid of the first supercritical reactor is oxygenated and then enters a self-preheating constant-temperature pipeline reactor for oxidation reaction, the self-preheating constant-temperature pipeline reactor is kept at a constant temperature by adjusting the circulating water quantity, and the reaction fluid of the first supercritical reactor is discharged for heating of the first preheating heat exchanger after oxidation reaction; and (3) oxidizing the reaction fluid of the second supercritical reactor, then, introducing the reaction fluid into a self-preheating constant-temperature pipeline reactor for oxidation reaction, and keeping the constant temperature in the self-preheating constant-temperature pipeline reactor by adjusting the circulating water quantity, and discharging the reaction fluid of the second supercritical reactor for heating of a multi-flow heat exchanger after oxidation reaction.
7. The zero-emission treatment process for volatile phenol in salt-containing wastewater according to claim 6, wherein the reaction fluid of the first supercritical reactor and the reaction fluid of the second supercritical reactor enter a self-preheating constant temperature pipeline reactor for reaction after COD is regulated by adding organic matters.
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| JPH09314155A (en) * | 1996-03-25 | 1997-12-09 | Japan Organo Co Ltd | Method and apparatus for oxidizing supercritical water |
| CN101987750A (en) * | 2010-10-22 | 2011-03-23 | 西安交通大学 | Pre-desalting machine for processing supercritical water of waste organic matters |
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