CN115340238A - Method and system device for treating high-salt volatile organic wastewater - Google Patents
Method and system device for treating high-salt volatile organic wastewater Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000001704 evaporation Methods 0.000 claims abstract description 148
- 230000008020 evaporation Effects 0.000 claims abstract description 144
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- 238000003860 storage Methods 0.000 claims description 16
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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
-
- 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
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention provides a method and a system device for treating high-salt volatile organic wastewater, which belong to the field of sewage treatment and comprise the following steps: pretreating high-salt volatile organic wastewater; pumping the pretreated wastewater, an acid regulator and an alkali regulator into a pipeline mixer, and controlling the hydrogen ion concentration of the wastewater; conveying the mixed liquid in the pipeline mixer to an evaporation reactor, and controlling the adding mode, the evaporation temperature and the evaporation time of persulfate; mixing the evaporated steam with ozone, passing through a condensing device, and then introducing into condensed water to secondarily degrade volatile organic compounds; the tail gas after reaction is purified and then is introduced into an evaporation reactor for recycling, and the distilled water after reaction can be used as condensed water or discharged. The invention realizes the gas-liquid two-phase synchronous oxidation of the high-salt volatile organic wastewater in the evaporation process, greatly shortens the treatment process flow, improves the utilization rate of resources, and ensures that the distilled water completely meets the recycling and emission standards.
Description
The application is a divisional application of Chinese patent application with the application number of 201910680992.X, which is filed by the intellectual Property office of China on the application date of 2019, 07, 26 and named as 'a method and a system device for treating high-salt volatile organic wastewater'.
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a method and a system device for treating high-salt volatile organic wastewater.
Background
The high-salt volatile organic wastewater contains more than 1 percent of total salt and a large amount of K + 、Na + 、Ca + 、SO 4 2- 、Cl - 、CO 3 2- Free inorganic ions, a large amount of organic components such as phthalic acid, formaldehyde, medium and low carbon alkane and the like, and has the characteristics of complex components, toxicity, peculiar smell, large chromaticity and poor biodegradability. The main source of the wastewater is high-salt water generated in the production processes of petrochemical industry, coal chemical industry, medicine, printing and dyeing and the like and other wastewater treatment processes such as electrodialysis, nanofiltration membrane, reverse osmosis and the like, and particularly shale gas fracturing flowback fluid causes great pollution to the environment if not properly treated.
The evaporation technology is gradually paid attention to in the field of treatment of high-salt volatile organic wastewater, and the high-salt volatile organic wastewater is directly evaporated and desalted. However, the evaporation technology cannot remove organic matters, volatile organic matters in the wastewater are condensed into distilled water along with water vapor due to temperature rise and entrainment, the quality of the distilled water is affected, pure distilled water cannot be obtained, and meanwhile, the organic matters can increase corrosion and scaling of an evaporation reactor.
Or preparing an organic matter treatment device before evaporation, and then performing desalination treatment, namely degrading the organic matters and then performing deep desalination by a thermal method. In this way, the evaporation temperature is increased, and distilled water with high yield is obtained, but the scaling possibility of equipment is increased; and the pretreatment requirements of various processes are different, and the series connection of various processes leads the process flow to be more tedious, the investment to be increased and the site requirement to be increased.
And the sulfur-containing gas field water is subjected to coagulation desulfurization and organic matter removal, the ammonia nitrogen is degraded by an oxidant, and evaporation is used as a desalting and advanced treatment process. For example, the process flow of the high-salt organic produced water of a certain natural gas field in Sichuan comprises the steps of chemical precipitation, steam stripping, coagulation and sedimentation and sectional evaporation. A process for treating the water generated by the high-salt organic shale gas in the Waterberg oilfield in the northeast of Dou roller includes three-phase separation, deposition softening, walnut shell filtering and membrane distillation. The processes are all carried out by separating organic matters from desalination, and have the technical problem of long process flow.
The advanced oxidation technology is also called as deep oxidation technology, is characterized by generating free radicals (hydroxyl free radicals, sulfuric acid free radicals and the like) with strong oxidation capacity, can completely mineralize or decompose most organic matters under the reaction conditions of high temperature and high pressure, electricity, sound, light irradiation, catalysts and the like, and has good application prospect. However, in the presence of inorganic salts, free radicals may be formed with Cl-, CO 3 2- 、HCO 3 - And quenching to affect the degradation of organic matters, so that the organic matters are more remained.
With the proposal of the concept of zero emission, the standard degree of sewage treatment is further improved. How to treat high-salt volatile organic wastewater to meet the discharge requirement is required at present.
Disclosure of Invention
The invention aims to provide a method and a system device for treating high-salt volatile organic wastewater, and the method for treating the high-salt volatile organic wastewater adopts gas-liquid two-phase synchronous oxidation, so that distilled water meets the recycling and discharging standards, the energy consumption of free radical activation is reduced, the utilization rate of resources is improved, and the process flow is greatly shortened.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a method for treating high-salt volatile organic wastewater, which comprises the following steps:
(1) Preparing organic wastewater and raw materials, wherein SS in the organic wastewater is less than or equal to 10mg/L;
(2) Adding an acid regulator and an alkali regulator into the organic wastewater to form a mixed solution, wherein the pH value is 4-5;
(3) Adding persulfate, evaporating at 60-70 deg.c for 1.5-2.5 hr; COD in solution Cr And S 2 O 8 2- The mass concentration ratio is 4-5, and the mass concentration of persulfate is 5%;
(4) Introducing ozone, and carrying out a condensation treatment step after mixing and reacting steam and ozone in the solution; the mass concentration of the ozone is 20-40 mg/L;
(5) And crystallizing the concentrated water to obtain the product.
Preferably, the acid regulator is HCl or sulfuric acid.
Preferably, the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate.
Preferably, the persulfate is sodium persulfate.
Preferably, the pH in step (2) is 5.
Preferably, the evaporation temperature is 60 ℃; the water conservancy residence time is 2 hours.
Preferably, the step (4) further comprises a tail gas recycling step, wherein the tail gas recycling step is as follows: refluxing part of tail gas after reaction into the step (3) for recycling, and performing emission treatment on the tail gas meeting the emission conditions; the tail gas is a steam part which cannot be condensed; about 30% of tail gas flows back.
The invention provides a system device for treating high-salt volatile organic wastewater, which comprises a wastewater tank 1, a wastewater pump 2, an acid liquid tank, a lye tank, an acid liquid pump, a lye pump, a pipeline mixer 5, a persulfate solution tank 6, a metering pump 7, an ozone generator 8, a blower 9, an evaporation reactor 10, a crystallization device 11, a condensing device 13 and a distilled water storage tank 14; the waste water tank 1 is connected with a waste water pump 2, the waste water pump 2 is connected with a pipeline mixer 5, an acid liquid tank is connected with an acid liquid pump, a base liquid tank is connected with a base liquid pump, the acid liquid pump and the base liquid pump are respectively connected with the pipeline mixer 5, and the pipeline mixer 5 is connected with an evaporation reactor 10; the persulfate solution tank 6 is connected with the metering pump 7, and the metering pump 7 is connected with the evaporation reactor 10; the crystallization device 11 is connected with the evaporation reactor 10, the ozone generator 8 is connected with the evaporation reactor 10 through the blower 9, the distilled water storage tank 14 is connected with the condensing device 13, and the condensing device 13 is connected with the evaporation reactor 10.
Preferably, the system device is also provided with a wastewater pretreatment device 19, and the pretreatment device 19 is connected with the wastewater tank 1.
Preferably, a tail gas pipe 16 is further provided, one end of the tail gas pipe 16 is connected with the distilled water storage tank 14, and the other end of the tail gas pipe 16 is connected between the blower 9 and the evaporation reactor 10.
The invention provides a method for treating high-salt volatile organic wastewater, which comprises the following steps: (1) Preparing organic wastewater and raw materials, wherein SS in the organic wastewater is less than or equal to 10mg/L; (2) Adding an acid regulator and an alkali regulator into the organic wastewater to form a mixed solution, wherein the pH value is 4-5; (3) Adding persulfate, and evaporating at the evaporation temperature of 60 ℃ for 1.5-2.5 h; COD in solution Cr And S 2 O 8 2- The mass concentration ratio is 4-5, and the mass concentration of persulfate is 5%; (4) Introducing ozone, and carrying out a condensation treatment step after mixing and reacting steam and ozone in the solution; the mass concentration of the ozone is 20-40 mg/L; and (5) crystallizing the concentrated water.
In the invention, the step (1) can greatly reduce the scaling possibility of evaporation equipment and ensure the stable operation of the equipment.
The step (2) mainly controls the generation amount and the generation type of free radicals, and simultaneously reduces the formation of carbonate scales. When the pH value in the step (2) is 4-5, persulfate is added in the step (3) to activate to generate a large amount of sulfuric acid free radicals with extremely strong oxidizability, and the requirement on equipment is not high; when the pH value is more than 5, the generation amount of the sulfuric acid free radical is gradually reduced, the generation amount of the hydroxyl free radical with relatively low oxidation capability is gradually increased, and the hydrolysis of the sulfuric acid free radical is accelerated under the alkaline condition, so that more hydroxyl free radicals are generated; when the pH value is less than 4, the requirement on corrosion resistance of equipment is higher, and a large amount of acid regulator needs to be added, so that the operation cost is increased.
And (3) mainly controlling the generation rate of free radicals of sulfuric acid and reducing the overflow of volatile organic compounds. At the temperature of 60-70 ℃, the generation rate of free radicals of sulfuric acid is accelerated, the content of volatile organic compounds in the gas is low, and the equipment is not suitable for scaling when stably running. When the temperature is higher than 70 ℃, a large amount of volatile organic compounds in the gas overflow, the concentration of the organic compounds in the liquid phase is reduced, the concentration of the oxidant relative to the organic compounds is increased, the oxidation efficiency is reduced, the concentration of the organic compounds in the distilled water is increased, the discharge requirement cannot be met, and the scaling possibility of equipment is increased. When the temperature is lower than 60 ℃, the generation efficiency of free radicals of sulfuric acid is low, organic matters in a liquid phase cannot be oxidized sufficiently, and the yield of distilled water is low, so that the desalting effect cannot be achieved.
And (3) mainly controlling the concentration ratio of the organic matters to persulfate, and improving the oxidation efficiency of the organic matters. At COD Cr And S 2 O 8 2- The mass concentration ratio is 4-5, and the removal rate of the organic matter is the highest when the mass fraction of the persulfate is 5%. Persulfate is a source of sulfuric acid free radicals, and when the concentration ratio of organic matters to persulfate is high, the concentration of persulfate is too low, the generation efficiency of the sulfuric acid free radicals is low, and the generation efficiency of the sulfuric acid free radicals is not enough to oxidize the organic matters in a liquid phase. When the concentration ratio of the organic matter to the persulfate is low, the persulfate concentration is too high, the sulfuric acid radical reacts with the persulfate, and the sulfuric acid radical is self-quenched, so that the concentration of the sulfuric acid radical is reduced, and the oxidation of the organic matter in the liquid phase is insufficient.
And (4) mainly controlling volatile organic compounds in the gas to ensure the stable water quality of the distilled water. When the ozone concentration is 20-40 mg/L, utilize steam thermocatalysis ozone oxidation gaseous state micro molecule organic matter, ozone tangential gets into the time that the evaporation reactor can increase ozone oxidation, and the mist inserts in the condensate water behind the condensing equipment, through the heterogeneous degree of depth oxidation condensate water organic matter of gas-liquid. When the concentration of the ozone is less than 20mg/L, volatile organic compounds in the gas are not oxidized sufficiently, and the condensed water cannot meet the emission requirement. When the ozone concentration is more than 40mg/L, the ozone concentration in the tail gas is too high, which causes resource waste and atmospheric pollution.
The pure salt is mainly obtained in the step (5). The organic matter in the brine can influence the quality of the salt, the organic matter in the high-salt organic wastewater is degraded and concentrated through the evaporation reactor to obtain pure strong brine, and then the pure high-quality salt is obtained through crystallization.
Further, in the present invention, the step (4) further includes a tail gas recycling step, and the tail gas recycling step includes: part of tail gas after reaction is refluxed and enters the step (3) for recycling, and the tail gas meeting the emission condition is subjected to emission treatment; the tail gas is a steam part which cannot be condensed; about 30% of tail gas flows back. And the tail gas recycling step mainly controls the recycling of the tail gas. About 30% of tail gas refluxes, ozone can be fully utilized, and the oxidation of gas-phase organic matters is enhanced. When the backflow of the tail gas is less than 30%, the concentration of ozone in the tail gas is too high, so that resource waste and atmospheric pollution are caused. When the reflux of the tail gas is more than 30%, the air amount entering the reactor is excessive, and the concentration of ozone in the gas phase of the reactor is reduced, so that volatile organic compounds in the gas are not oxidized sufficiently, and condensed water cannot meet the emission requirement.
Further, in the present invention, the persulfate is sodium persulfate. When the dosage needs to be large, potassium persulfate can not be completely dissolved, ammonium persulfate can possibly cause the problem of rising of ammonia nitrogen in distilled water, and sodium persulfate is the most suitable persulfate.
The invention provides a system device for treating high-salt volatile organic wastewater, which comprises a wastewater tank 1, a wastewater pump 2, an acid liquid tank, a lye tank, an acid liquid pump, a lye pump, a pipeline mixer 5, a persulfate solution tank 6, a metering pump 7, an ozone generator 8, a blower 9, an evaporation reactor 10, a crystallization device 11, a condensing device 13 and a distilled water storage tank 14; the waste water tank 1 is connected with a waste water pump 2, the waste water pump 2 is connected with a pipeline mixer 5, the acid liquid tank is connected with an acid liquid pump, the alkali liquid tank is connected with an alkali liquid pump, the acid liquid pump and the alkali liquid pump are respectively connected with the pipeline mixer 5, and the pipeline mixer 5 is connected with an evaporation reactor 10; the persulfate solution tank 6 is connected with the metering pump 7, and the metering pump 7 is connected with the evaporation reactor 10; the crystallization device 11 is connected with the evaporation reactor 10, the ozone generator 8 is connected with the evaporation reactor 10 through the blower 9, the distilled water storage tank 14 is connected with the condensing device 13, and the condensing device 13 is connected with the evaporation reactor 10. In the present invention, distilled water is recovered from the distilled water tank 14, tail gas is also discharged from the distilled water tank 14, and pure salt is obtained from the crystallization device 11.
According to the invention, a gas-liquid two-phase synchronous oxidation technology is adopted to continuously oxidize volatile organic compounds in different phase states of the same evaporation reactor, the organic compounds are synchronously removed in the evaporation desalting process, the volatile organic compounds in the evaporation process are controlled by gas phase oxidation, part of tail gas is refluxed to fully utilize ozone in the tail gas, part of distilled water is condensed and recycled, and the rest of distilled water can be directly discharged.
According to the invention, persulfate is added into the evaporation reactor, and the evaporation heat is utilized to activate the oxidant to generate free radicals, so that volatile organic matters are oxidized, and in order to ensure the water quality of distilled water, ozone is added into steam to oxidize the organic matters carried out by entrainment, thereby realizing desalination and removing the organic matters, and greatly shortening the process flow.
The invention adopts persulfate and ozone as oxidants to realize effective removal of gas-liquid two-phase organic matters in the evaporation process of high-salt volatile organic wastewater, uses heat in the evaporation process for generating free radicals, thereby decomposing the organic matters in the evaporation process, ensuring the quality of distilled water, simultaneously reducing the energy consumption of free radical activation, adding ozone in a gas phase to control the volatile organic matters to enter the distilled water, and deeply oxidizing in the distilled water, greatly shortening the process flow, saving the cost, leading the distilled water to completely meet the recycling and discharging standards, and leading the concentration of the volatile organic matters in the gas to be less than the detection limit.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic diagram of an apparatus optimized in the present invention;
1. the system comprises a waste water tank, 2. A waste water pump, 3. An acid liquid tank and a lye tank, 4. An acid liquid pump and a lye pump, 5. A pipeline mixer, 6. A persulfate solution tank, 7. A metering pump, 8. An ozone generator, 9. A blower, 10. An evaporation reactor, 11. A crystallization device, 12. Strong brine, 13. A condensing device, 14. A distilled water storage tank, 15. Condensation recycling, 16. A tail gas pipe, 17. Ozone recycling, 18. A water outlet and 19. A pretreatment device.
Detailed Description
The invention provides a method for treating high-salt volatile organic wastewater, which comprises the following steps:
(1) Preparing organic wastewater and raw materials, wherein SS in the organic wastewater is less than or equal to 10mg/L;
(2) Adding an acid regulator and an alkali regulator into the organic wastewater to form a mixed solution, wherein the pH value is 4-5;
(3) Adding persulfate, evaporating at 60-70 deg.c for 1.5-2.5 hr; COD in solution Cr And S 2 O 8 2- The mass concentration ratio is 4-5, and the mass concentration of persulfate is 5%;
(4) Introducing ozone, and carrying out a condensation treatment step after mixing and reacting steam and ozone in the solution; the mass concentration of the ozone is 20-40 mg/L;
(5) And crystallizing the concentrated water to obtain the product.
In the invention, in the step (1), the high-salt volatile organic wastewater is preferably shale gas fracturing flowback fluid.
In the present invention, in the step (3), the addition is preferably performed 1 time every 60 min.
In the present invention, in the step (3), the persulfate may be added simultaneously with the evaporation, or may be added before or after the evaporation.
In the present invention, in the step (5), the concentrated water is obtained by evaporation.
In the invention, the tail gas reflux is to increase the utilization rate of ozone and carry out secondary oxidation to ensure that the tail gas reaches the standard and is discharged.
The invention provides a system device for treating high-salt volatile organic wastewater. In the invention, the equipment devices are connected through pipelines. The various tanks, instruments and devices used, as well as the reactors, are of conventional equipment and construction.
In order to further illustrate the present invention, the following detailed description of the technical solutions provided by the present invention is made with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A gas-liquid two-phase synchronous oxidation method for treating high-salt volatile organic wastewater comprises the following steps:
(1) Pretreating high-salt volatile organic wastewater to ensure that SS (suspended solid) in the wastewater is lower than 10mg/L; the pretreatment method can adopt a membrane treatment mode, can also adopt a coagulation mode to treat, and can also adopt a filtration mode. The membrane treatment, coagulation or filtration mode is a conventional wastewater pretreatment mode.
(2) Pumping the organic wastewater, an acid regulator and an alkali regulator into a pipeline mixer, and controlling the initial pH of the wastewater to be 4.5;
(3) According to the Chemical Oxygen Demand (COD) Cr And S 2 O 8 2- Pumping persulfate with the mass fraction of 5 percent into the evaporation reactor according to the mass concentration ratio of 4.5;
(4) Conveying the mixed liquid in the pipeline mixer to an evaporation reactor, and controlling the evaporation temperature to be 65 ℃;
(5) Mixing the evaporated steam with ozone with the concentration of 30mg/L for reaction, carrying out thermal catalysis on the ozone by using the steam to oxidize gaseous micromolecule organic matters, introducing the mixed gas into condensed water after the mixed gas passes through a condensing device, and deeply oxidizing the organic matters in the condensed water through gas-liquid heterogeneous phase; ozone is introduced above the liquid level of the evaporation reactor along the tangential direction of the evaporation reactor through a blower, so that evaporation steam and gas are mixed and reacted, the mixed gas passes through a condensing device and then is introduced into condensed water, and volatile organic compounds are secondarily degraded;
(6) 30% of tail gas after reaction flows back to enter an evaporation reactor for recycling, distilled water after reaction can be used as condensate for recycling or discharge, the COD (chemical oxygen demand) value of waste water is less than 60mg/L, and the concentration of volatile organic compounds in gas is less than the detection limit.
Example 2
A gas-liquid two-phase synchronous oxidation system device for treating high-salt volatile organic wastewater is provided with a wastewater tank 1, a wastewater pump 2, an acid liquid tank, a lye tank, an acid liquid pump, a lye pump, a pipeline mixer 5, a persulfate solution tank 6, a metering pump 7, an ozone generator 8, a blower 9, an evaporation reactor 10, a crystallization device 11, a condensation device 13 and a distilled water storage tank 14; the waste water tank 1 is connected with a waste water pump 2, the waste water pump 2 is connected with a pipeline mixer 5, an acid-base liquid tank is connected with an acid-base liquid pump, the acid-base liquid pump and a base liquid pump are connected with the pipeline mixer 5, and the pipeline mixer 5 is connected with an evaporation reactor 10; the persulfate solution tank 6 is connected with the metering pump 7, and the metering pump 7 is connected with the evaporation reactor 10; the crystallization device 11 is connected with the evaporation reactor 10, the ozone generator 8 is connected with the evaporation reactor 10 through the blower 9, the distilled water storage tank 14 is connected with the condensing device 13, and the condensing device 13 is connected with the evaporation reactor 10.
Distilled water is recovered from the distilled water tank 14 and off-gas is also discharged from the distilled water tank 14 and pure salt is obtained from the crystallization device 11.
Example 3
A gas-liquid two-phase synchronous oxidation system device for treating high-salinity volatile organic wastewater is provided with a wastewater pretreatment device 19, a wastewater tank 1, a wastewater pump 2, an acid liquid tank, a lye tank, an acid liquid pump, a lye pump, a pipeline mixer 5, a persulfate solution tank 6, a metering pump 7, an ozone generator 8, a blower 9, an evaporation reactor 10, a crystallization device 11, a condensation device 13, a distilled water storage tank 14 and a tail gas pipe 16, wherein the wastewater pretreatment device 19 is connected with the wastewater tank 1, the wastewater tank 1 is connected with the wastewater pump 2, the wastewater pump 2 is connected with the pipeline mixer 5, the acid lye tank is connected with the acid liquid pump, the acid liquid pump and the lye pump are connected with the pipeline mixer 5, and the pipeline mixer 5 is connected with the evaporation reactor 10; the persulfate solution tank 6 is connected with the metering pump 7, and the metering pump 7 is connected with the evaporation reactor 10; the crystallization device 11 is connected with the evaporation reactor 10, the ozone generator 8 is connected with the evaporation reactor 10 through the blower 9, the distilled water storage tank 14 is connected with the condensing device 13, and the condensing device 13 is connected with the evaporation reactor 10; one end of the tail gas pipe 16 is connected with the distilled water storage tank 14, and the other end connection point is arranged between the blower 9 and the evaporation reactor 10. The equipment devices are connected through pipelines.
Distilled water is recovered from the distilled water storage tank 14, tail gas is discharged from the tail gas pipe 16, and pure salt is obtained from the crystallization device 11.
The operation steps of the system device in use are as in example 1. The system can adopt a continuous evaporation mode, namely, the system can simultaneously evaporate and crystallize, and concentrated water is always led to the crystallization device. Continuous evaporation means that waste water is always introduced into an evaporation reactor to generate concentrated water and fresh water all the time, crystallization is always carried out, and gas recovery is also always carried out. Continuous evaporation is carried out while adding.
Or intermittent evaporation instead of continuous evaporation, wherein gas is introduced and recovered all the time in the evaporation process, and concentrated water is introduced into a crystallization device for crystallization after evaporation is finished. The addition of the medicament is added before evaporation, and the addition amount is added according to the same proportion as that of continuous evaporation.
The used tanks, instruments and devices, and reactors are all conventional equipment and structures, such as a condensing device 13 which is an LJEP-NFDK type condensed water recovery device, and an evaporation reactor 10 which is an HC-DX evaporator reactor; the crystallization device 11 is a DBT type crystallizer, and the ozone generator 8 is a CF-G-2 ozone generator. The same applies hereinafter.
Example 4
After pretreatment 19, SS in the wastewater is reduced to 7mg/L from 74mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr Concentration 546mg/L, cl - The high-salt organic wastewater with the content of 21860mg/L and the pH =7.5 is pumped into a pipeline mixer 5, and HCl in the 1. The evaporation temperature of the evaporation reactor is controlled to be 60 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- The persulfate solution with the mass fraction of 5 percent in the persulfate solution tank is added into the evaporation reactor 10 according to the mass concentration ratio of 5, and the mass fraction of the persulfate solution is 109.2mg/L. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam has been passed through the condensation device 13,the obtained distilled water enters a distilled water storage tank 14 and can be recycled 15 in a condensing device or directly discharged 18, and the ozone in the tail gas is introduced into the steam in the evaporation reactor for recycling through a tail gas pipe 16. COD in the brine entering the crystallization device 11 is 87mg/L and Cl - The content was 47642mg/L and the COD in the distilled water 14 was 41mg/L.
Example 5
After pretreatment of 19, SS in the wastewater is reduced from 84mg/L to 6mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr The concentration is 233mg/L, cl - The high-salt organic wastewater with the content of 24220mg/L and the pH =7.5 is pumped into a pipeline mixer 5, and HCl in the 1. The evaporation temperature of the evaporation reactor is controlled to be 60 ℃, and the hydraulic retention time is 2 hours. According to COD Cr And S 2 O 8 2- And (3) adding 109.2mg/L of persulfate with the mass fraction of 5% in a persulfate solution tank into the evaporation reactor 10 according to the mass concentration ratio of 5. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 71mg/L and Cl - The content is 50920mg/L, and the COD in the distilled water 14 is 38mg/L.
Example 6
After pretreatment 19, SS in the wastewater is reduced from 166mg/L to 8mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr Concentration 1428mg/L, cl - The high-salt organic wastewater with the content of 18220mg/L and the pH =6.5 is pumped into a pipeline mixer 5, and HCl in the 1. The evaporation temperature of the evaporation reactor is controlled to be 70 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- Persulfate is added into the evaporation reactor 10 according to the mass concentration ratio of 5The mass fraction of the persulfate in the solution tank is 357mg/L of 5 percent. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. And (3) after the steam passes through a condensing device 13, obtaining distilled water 14 which can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas is introduced into the steam in the evaporation reactor through a tail gas pipe 16 for recycling 17 the ozone. COD in the brine entering the crystallization device 11 is 45mg/L and Cl - The content was 52648mg/L, and the COD in the distilled water 14 was 57mg/L.
Example 7
After pretreatment 19, SS in the wastewater is reduced to 8mg/L from 182mg/L, and then the wastewater is introduced into a wastewater tank to discharge COD in the sewage pump 2 Cr The concentration was 899mg/L, cl - The high-salt organic wastewater with the content of 20618mg/L and the pH =7 is pumped into a pipeline mixer 5, and HCl of 1 in an acid liquid tank and a lye liquid tank 3 is pumped into the pipeline mixer to be fully mixed, so that the pH of the wastewater is adjusted to be 4. The evaporation temperature of the evaporation reactor is controlled to be 70 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- The persulfate solution with the mass fraction of 5 percent in the persulfate solution tank is added into the evaporation reactor 10 according to the mass concentration ratio of 4, and the mass fraction of 224.8mg/L is added. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 27mg/L and Cl - The content was 59208mg/L, and the COD in the distilled water 14 was 46mg/L.
Example 8
After pretreatment 19, SS in the wastewater is reduced to 7mg/L from 109mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr Concentration 1104mg/L, cl - Pumping the high-salt organic wastewater with the content of 23323mg/L and the pH =7 into a pipeline mixer 5, pumping HCl in 1The pH of the waste water is 4. The evaporation temperature of the evaporation reactor is controlled to be 70 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- 276mg/L of persulfate with the mass fraction of 5% in a persulfate solution tank is added into the evaporation reactor 10 according to the mass concentration ratio of 4. Meanwhile, ozone with the concentration of 40mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 17, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 31mg/L and Cl - The content is 65614mg/L, and the COD in the distilled water 14 is 25mg/L.
Example 9
After pretreatment 19, SS in the wastewater is reduced from 74mg/L to 7mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr The concentration is 546mg/L, cl - High salt organic waste water with a content of 21860mg/L, pH =7.5 was pumped into a pipe mixer 5. The evaporation temperature of the evaporation reactor is controlled to be 60 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- The persulfate solution with the mass fraction of 5 percent in the persulfate solution tank is added into the evaporation reactor 10 according to the mass concentration ratio of 5, and the mass fraction of the persulfate solution is 109.2mg/L. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 94mg/L and Cl - The content was 47642mg/L and the COD in the distilled water 14 was 83mg/L.
Example 10
After pretreatment of 19, SS in the wastewater is reduced from 84mg/L to 6mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr Concentration 233mg/L, cl - Pumping high-salt organic wastewater with the content of 24220mg/L and the pH =7.5 into a pipeline mixer5, and (3). The evaporation temperature of the evaporation reactor is controlled to be 50 ℃, and the hydraulic retention time is 2 hours. According to COD Cr And S 2 O 8 2- The persulfate solution with the mass fraction of 5 percent in the persulfate solution tank is added into the evaporation reactor 10 according to the mass concentration ratio of 5, and the mass fraction of the persulfate solution is 109.2mg/L. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 85mg/L and Cl - The content was 36840mg/L, and the COD in the distilled water 14 was 69mg/L.
Comparative example 1
After pretreatment 19, SS in the wastewater is reduced to 8mg/L from 182mg/L, and then the wastewater is introduced into a wastewater tank to discharge COD in the sewage pump 2 Cr Concentration 899mg/L, cl - The high-salt organic wastewater with the content of 20618mg/L and the pH =7 is pumped into a pipeline mixer 5, and HCl of 1 in an acid liquid tank and a lye liquid tank 3 is pumped into the pipeline mixer to be fully mixed, so that the pH of the wastewater is adjusted to be 4. The evaporation temperature of the evaporation reactor is controlled to be 50 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- Adding 168.6mg/L persulfate with the mass fraction of 5% in a persulfate solution tank into the evaporation reactor 10 according to the mass concentration ratio of 3. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 124mg/L and Cl - The content was 31208mg/L, and the COD in the distilled water 14 was 106mg/L.
Comparative example 2
After pretreatment 19, SS in the wastewater is reduced to 8mg/L from 182mg/L, and then the wastewater is introduced into a wastewater tank to discharge COD in the sewage pump 2 Cr The high-salt organic wastewater with the concentration of 899mg/L, the Cl < - > content of 20618mg/L and the pH =7 is pumped into a pipeline mixer 5, and HCl in an acid liquid tank and an alkali liquid tank 3 is pumped into the pipeline mixer to be fully mixed, so that the pH of the wastewater is adjusted to be 5. The evaporation temperature of the evaporation reactor is controlled to be 70 ℃, and the hydraulic retention time is 2 hours. According to the COD Cr And S 2 O 8 2- Adding 168.6mg/L of persulfate with the mass fraction of 5% in a persulfate solution tank into the evaporation reactor 10 according to the mass concentration ratio of 3. Meanwhile, ozone with the concentration of 15mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. The COD in the brine entering the crystallization device 11 is 118mg/L, the Cl-content is 59208mg/L, and the COD in the distilled water 14 is 146mg/L.
Comparative example 3
After pretreatment 19, SS in the wastewater is reduced to 8mg/L from 182mg/L, and then the wastewater is introduced into a wastewater tank to discharge COD in the sewage pump 2 Cr The high-salt organic wastewater with the concentration of 899mg/L, the Cl < - > content of 20618mg/L and the pH =7 is pumped into a pipeline mixer 5, and HCl in an acid liquid tank and an alkali liquid tank 3 is pumped into the pipeline mixer to be fully mixed, so that the pH of the wastewater is adjusted to 4. The evaporation temperature of the evaporation reactor is controlled to be 50 ℃, and the hydraulic retention time is 1 hour. According to the COD Cr And S 2 O 8 2- Adding 168.6mg/L of persulfate with the mass fraction of 5% in a persulfate solution tank into the evaporation reactor 10 according to the mass concentration ratio of 3. Meanwhile, ozone with the concentration of 20mg/L generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through a tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 267mg/L, cl-content is 28830mg/L, and COD in the distilled water 14 is 116mg/L.
Comparative example 4
After being pretreated by 19, SS in the wastewater is reduced to 7mg/L from 109mg/L, and then the wastewater is introduced into a wastewater tank to remove COD in the sewage pump 2 Cr The high-salt organic wastewater with the concentration of 1104mg/L, the Cl < - > content of 23323mg/L and the pH =7 is pumped into a pipeline mixer 5, naOH in an acid liquid tank and an alkali liquid tank 3 is pumped into the pipeline mixer at the same time, and the NaOH is fully mixed in the ratio of 1. The evaporation temperature of the evaporation reactor is controlled to be 50 ℃, and the hydraulic retention time is 2 hours. According to COD Cr And S 2 O 8 2- The persulfate solution with the mass fraction of 5 percent is added into the evaporation reactor 10 according to the mass concentration ratio of 3, and 207mg/L of persulfate is added into the evaporation reactor 10. Meanwhile, 15mg/L ozone generated by the ozone generator 8 is added into the steam in the evaporation reactor 10, and micromolecular organic matters in the steam are continuously oxidized. After the steam passes through the condensing device 13, the obtained distilled water 14 can be recycled 15 in the condensing device or directly discharged 18, and the ozone in the tail gas passes through the tail gas pipe 16 and then is introduced into the steam in the evaporation reactor for recycling. COD in the brine entering the crystallization device 11 is 384mg/L and Cl - The content was 29140mg/L, and the COD in the distilled water 14 was 182mg/L.
Comparative example 5
COD Cr Concentration 898mg/L, cl - After high-salt organic wastewater with the content of 27410mg/L and the pH =9.14 is subjected to chemical precipitation, stripping, coagulation sedimentation and sectional evaporation treatment, COD in distilled water at the first stage is 1883mg/L and is not removed, the content of the distilled water at the second stage can be reduced to 44mg/L, COD in concentrated water is still 460mg/L, and the process does not realize complete removal of pollutants. In addition, except for the evaporation process, the operation investment of the pretreatment process only removing SS in the invention can be saved by at least 50% compared with the operation investment of the process for removing sulfide, SS and inorganic ions by two-stage precipitation and stripping, and the treatment time can be reduced by at least 2/3.
Comparative example 6
COD Cr Concentration 1520mg/L, cl - High-salt organic wastewater with the content of 23292mg/L and the pH =6.6 is subjected to three-phase separation, precipitation softening, walnut shell filtration and membrane steamingAfter distillation, the COD in the distilled water is 76mg/L, the requirement that the COD in the distilled water is less than 60mg/L is not met, the construction cost of a long pretreatment device before distillation is higher than that of the invention, the treatment time is increased by more than 50%, the operation cost of the filter filler and the cleaning and replacing of the membrane is increased by more than 20%, and the removal of concentrated water is not considered.
Different oxidant adding amounts, evaporation temperatures, reaction times and pH values are direct factors influencing the generation of free radicals and the degradation efficiency of organic matters. Therefore, proper process combination, process condition selection and equipment improvement are the key points for treating the high-salt volatile organic wastewater. In the invention, for persulfate advanced oxidation technology, the generation of free radicals is influenced due to too high addition of persulfate, so that the degradation efficiency of organic matters is influenced, the oxidant is rapidly consumed due to too low addition, the organic matters are incompletely oxidized, a large amount of micromolecule organic matters with strong volatility are generated, and the quality of condensed water is influenced, so that the addition of a proper amount of persulfate is the key for removing the organic matters.
The pH value also affects the generation of free radicals, in addition, the types of the free radicals generated are different according to different pH values, the oxidation efficiency of different types of the free radicals to organic matters is greatly different, and the control of the pH value and the adding amount of the oxidant is the main reason for the degradation of the organic matters. According to the invention, the conditions of the persulfate adding amount and the pH value are optimized, so that the generation of strong oxidizing free radicals is realized, the high degradation rate of organic matters is ensured, and the generation and overflow of volatile organic matters are reduced.
In the invention, high-salt volatile organic wastewater is pretreated, the pretreated wastewater and an acid-base regulator are pumped into a pipeline mixer, and the hydrogen ion concentration of the wastewater is controlled; conveying the mixed liquid in the pipeline mixer to an evaporation reactor, and controlling the adding mode, the evaporation temperature and the evaporation time of persulfate; mixing the evaporated steam with ozone, passing through a condensing device, and then introducing into condensed water to secondarily degrade volatile organic compounds; purifying the tail gas after reaction, then introducing the tail gas into an evaporation reactor for recycling, wherein the distilled water after reaction can be used as condensed water or discharged, and the concentrated water is crystallized to prepare salt.
While the foregoing shows and describes the fundamental principles and principal features of the invention, together with the advantages thereof, the foregoing description of the embodiments and description is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the spirit and scope of the invention, which will fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for treating high-salt volatile organic wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing organic wastewater and raw materials, wherein SS in the organic wastewater is less than or equal to 10mg/L;
(2) Adding an acid regulator and an alkali regulator into the organic wastewater to form a mixed solution, wherein the pH value is 4-5;
(3) Adding persulfate, evaporating at 60-70 deg.c for 1.5-2.5 hr; COD in solution Cr And S 2 O 8 2- The mass concentration ratio is 4-5, and the mass concentration of persulfate is 5%;
(4) Introducing ozone, and carrying out a condensation treatment step after mixing and reacting steam and ozone in the solution; the mass concentration of the ozone is 20-40 mg/L;
(5) And crystallizing the concentrated water to obtain the product.
2. The method for treating high-salinity volatile organic wastewater according to claim 1, wherein the method comprises the following steps: the acid regulator is HCl or sulfuric acid.
3. The method for treating high-salt volatile organic wastewater according to claim 1, characterized in that: the persulfate is one or more than two of sodium persulfate, potassium persulfate and ammonium persulfate.
4. A method for treating high-salinity volatile organic wastewater according to claim 1 or 3, characterized in that: the persulfate is sodium persulfate.
5. The method for treating high-salt volatile organic wastewater according to claim 1, characterized in that: the pH value in the step (2) is 5.
6. The method for treating high-salinity volatile organic wastewater according to claim 1, wherein the method comprises the following steps: the evaporation temperature is 60 ℃; the water conservancy residence time is 2 hours.
7. The method for treating high-salt volatile organic wastewater according to claim 1, characterized in that: the step (4) also comprises a tail gas recycling step, wherein the tail gas recycling step comprises the following steps: refluxing part of tail gas after reaction into the step (3) for recycling, and performing emission treatment on the tail gas meeting the emission conditions; the tail gas is a steam part which cannot be condensed; about 30 percent of tail gas reflows.
8. The utility model provides a handle high salt volatile organic waste water's system's device which characterized in that: comprises a wastewater tank (1), a wastewater pump (2), an acid liquid tank, a lye tank, an acid liquid pump, a lye pump, a pipeline mixer (5), a persulfate solution tank (6), a metering pump (7), an ozone generator (8), a blower (9), an evaporation reactor (10), a crystallization device (11), a condensing device (13) and a distilled water storage tank (14); the waste water tank (1) is connected with a waste water pump (2), the waste water pump (2) is connected with a pipeline mixer (5), the acid liquid tank is connected with an acid liquid pump, the alkali liquid tank is connected with an alkali liquid pump, the acid liquid pump and the alkali liquid pump are respectively connected with the pipeline mixer (5), and the pipeline mixer (5) is connected with an evaporation reactor (10); the persulfate solution tank (6) is connected with the metering pump (7), and the metering pump (7) is connected with the evaporation reactor (10); the crystallization device (11) is connected with the evaporation reactor (10), the ozone generator (8) is connected with the evaporation reactor (10) through a blower (9), the distilled water storage tank (14) is connected with the condensing device (13), and the condensing device (13) is connected with the evaporation reactor (10).
9. The system device for treating high-salinity wastewater according to claim 8, wherein: the system device is also provided with a wastewater pretreatment device (19), and the pretreatment device (19) is connected with the wastewater tank (1).
10. The system device for treating high-salinity wastewater according to claim 8, wherein: and a tail gas pipe (16) is also arranged, one end of the tail gas pipe (16) is connected with the distilled water storage tank (14), and the other end connecting point is arranged between the blower (9) and the evaporation reactor (10).
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