CN115771977A - Method and apparatus for treating waste water containing organic pollutant - Google Patents
Method and apparatus for treating waste water containing organic pollutant Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Physical Water Treatments (AREA)
Abstract
The application provides a method and equipment for treating wastewater containing organic pollutants. The method comprises the following steps: separating water-insoluble organic matter from the wastewater by using magnetic Janus particles and magnetic field action; performing distillation to separate and recover a portion of the dissolved form of the organic matter in the wastewater; performing biochemical treatment, and degrading partial dissolved organic matters in the wastewater by using microorganisms; and carrying out catalytic oxidation by ozone to oxidize dissolved organic matters in the wastewater and difficult to degrade. The apparatus comprises: an oil-water separation unit, a distillation unit, a biochemical treatment unit and an ozone catalytic oxidation unit.
Description
Technical Field
The invention relates to the field of treatment of wastewater containing organic pollutants, in particular to the field of treatment of high-concentration COD (chemical oxygen demand) organic solvent wastewater, and particularly provides a method and equipment for treating wastewater containing organic pollutants.
Background
The consumption of petroleum and its derived products by industry causes great pollution to the environment. Oil slick caused by ocean oil leakage accidents, oily sewage generated by oil extraction and drilling, oil sludge formed on the inner wall of an oil storage tank, oil sand of a drilling platform and the like all cause great pressure on relevant sewage treatment. The sewage of a multiphase complex mixed system is difficult for environmental protection treatment, the traditional treatment mode is demulsification under the condition of a compound surfactant, and the small molecular surfactant is usually toxic and harmful and can cause secondary pollution to the environment.
The high-concentration COD organic solvent wastewater is one of sewage difficult to treat, has the outstanding problems of difficult treatment, high energy consumption, great pollution and the like, and becomes an important threat to the natural environment and the human health. At present, the traditional method for treating high-concentration COD organic solvent wastewater mainly depends on incineration, gas generated by the method easily causes secondary pollution, and meanwhile, the incineration energy consumption is huge, so that the method is not a green environmental protection technology.
The organic pollutants contained in the high-concentration COD organic solvent wastewater are various in types and different in properties, for example, organic matters (oily matters) which are insoluble in water, organic matters which can be dissolved in water and the like are included, and the organic pollutants with different properties are difficult to remove through a single wastewater treatment mode or equipment, namely the high-concentration COD organic solvent wastewater reaches the dischargeable standard through the single wastewater treatment mode or equipment.
Therefore, aiming at the waste water containing organic pollutants, in particular the waste water containing high-concentration COD organic solvent, the green solution which can efficiently remove various organic pollutants and realize the regeneration and resource treatment is urgently hoped to be provided.
Disclosure of Invention
Problems to be solved by the invention
The invention provides integrated sewage treatment equipment and a method capable of continuously separating or removing different organic pollutants.
The method comprises the steps of firstly treating the wastewater containing the organic matters by using the magnetic Janus particles and a matched device thereof, and removing an oil phase in the wastewater by using the emulsification of the magnetic Janus particles, wherein the oil phase comprises oil slick, emulsified oil, solid oily matters and the like. The step can realize the complete removal of the oil phase, and provides sufficient conditions for subsequent distillation treatment and biochemical treatment and ozone catalytic oxidation treatment. The treated waste water can be subjected to fractionation and recovery of partial soluble organic matters through a distillation device, and organic solvent resource regeneration is realized. After the wastewater is treated by the two stages, most organic matters are separated and recycled, but the organic matters which are still partially dissolved remain in the wastewater and are difficult to separate. And introducing the wastewater obtained through the two steps of treatment into a biochemical treatment device, and degrading and removing part of organic matters through biochemical treatment. And then the residual organic matters which are difficult to degrade in the wastewater are removed by introducing the wastewater into an ozone catalytic oxidation device and utilizing an oxidation technology. The COD value of the wastewater obtained through the series of treatments is greatly reduced, and most of organic solvents are separated and recovered.
Means for solving the problems
In a first aspect of the present invention, there is provided a method for treating wastewater containing organic contaminants, comprising: step 1: mixing magnetic Janus particles in waste water containing organic pollutants to obtain emulsion, and enabling emulsion droplets of the magnetic Janus particles serving as dispersed phases in the emulsion to migrate and/or be enriched under the action of a magnetic field, so that water-insoluble organic matters are separated from the waste water, and discharging a treatment solution 1;
step 2: distilling the treatment solution 1, separating and recovering part of dissolved organic matters, and discharging a treatment solution 2;
and step 3: performing biochemical treatment on the treatment solution 2, degrading partial dissolved organic matters by using microorganisms, and discharging the treatment solution 3;
and 4, step 4: the treatment liquid 3 was subjected to catalytic ozonation.
In some embodiments of the invention, step 1 comprises: forming magnetic Janus particles into an aqueous dispersion with the solid content of 1-20wt%, and mixing the aqueous dispersion with the wastewater to obtain a stable oil-in-water emulsion, wherein magnetic Janus particle emulsion droplets formed by coating water-insoluble organic matters on the magnetic Janus particles are used as a dispersion phase; using a magnet to cause migration and/or enrichment of the magnetic Janus particle emulsion droplets onto or near the magnet; discharging the continuous phase;
the dosage of the magnetic Janus particles relative to the wastewater containing organic pollutants is 0.01-20wt%.
The magnetic Janus particle is NH 2 -Fe 3 O 4 -C 8 And (3) granules.
The catalyst adopted in the step 4 is selected from Co-Mn/ZrO 2 A catalyst.
In a second aspect of the present invention, there is provided an apparatus for treating wastewater containing organic contaminants, comprising:
an oil-water separation unit: separating water-insoluble organic matters from the wastewater by using magnetic Janus particles and the action of a magnetic field;
a distillation unit: for separating partially dissolved form organics in the wastewater;
a biochemical treatment unit: for degrading partially dissolved form organic matter;
an ozone catalytic oxidation unit: used for catalytic oxidation of dissolved and refractory organics.
In some embodiments of the invention, in the oil-water separation unit, magnetic Janus particle emulsion droplets are migrated and/or enriched by the action of a magnetic field so as to separate water-insoluble organic matters;
the magnetic Janus particle emulsion droplets are dispersed phases formed by coating water-insoluble organic matters on magnetic Janus particles in emulsion obtained by emulsifying the wastewater by using the magnetic Janus particles as a solid emulsifier.
In some embodiments of the invention, the oil-water separation unit comprises a magnetically controlled oil-water separation device comprising a container capable of holding wastewater; and
a magnet configured to generate a magnetic force on the magnetic Janus particle emulsion droplet within the container.
Optionally, the magnet is fixedly configured or configured to be movable or rotatable.
In some embodiments of the invention, the distillation unit comprises a rectification column and a condenser.
The biochemical treatment unit comprises an anoxic tank, an aerobic tank and a sedimentation tank; a water inlet, a lift pump and a grid are arranged in the anoxic tank; the aerobic tank is internally provided with a water inlet weir, an aeration device, a reflux device, a water outlet weir and a biological filler;
the ozone catalytic oxidation unit comprises a control cabinet, a circulating water storage tank, a three-section aeration tower and an ozone generator, wherein a catalyst is loaded in the three-section aeration tower.
The third aspect of the present invention provides a method for treating wastewater containing organic pollutants, which comprises the steps of:
a step of separating water-insoluble organic substances from the wastewater by using magnetic Janus particles and the action of a magnetic field;
a step of distilling the treatment liquid obtained in the previous step to separate and recover a part of dissolved organic matters in the wastewater;
performing biochemical treatment on the treatment liquid obtained in the previous step, and degrading partial dissolved organic matters in the wastewater by using microorganisms;
and (3) carrying out catalytic ozonation on the treatment liquid obtained in the previous step to oxidize dissolved and difficultly degraded organic matters in the wastewater.
ADVANTAGEOUS EFFECTS OF INVENTION
The method and the equipment for treating the wastewater containing the organic pollutants can realize continuous gradual separation or removal of different organic pollutants contained in the wastewater and recovery of partial organic solvent, and are an integrated sewage treatment method and equipment. The method can efficiently realize the treatment of the high-concentration organic solvent wastewater, so that the high-concentration organic solvent wastewater reaches the discharge standard, and is green and environment-friendly.
The invention can realize the oil-water separation of the high-concentration COD organic solvent wastewater by using the magnetic Janus particles and corresponding matched equipment together, separate out water-insoluble organic solvents (such as oil-floating, emulsified oil and solid oil), and distill the wastewater discharged after treatment in a distillation tower, and can recover most of the dissolved organic solvents by distillation. Wherein, the magnetic Janus particles have no pollution to the environment and can be recycled.
Then, the residual wastewater enters a biochemical water treatment device to degrade part of the dissolved organic solvent, and the discharged wastewater enters an ozone catalytic oxidation device to degrade most of the residual dissolved organic matters. After the treatment by the technical route, the COD value of the high-concentration COD organic solvent wastewater can be greatly reduced, the separated partial solvent can be recycled, and the residual wastewater can be discharged up to the standard.
Drawings
FIG. 1: the technical route of the invention is shown schematically.
FIG. 2: (a) Is a schematic diagram of a magnetic control oil-water separation device in a specific scheme; (b) is an enlarged view of part A in (a); and (c) is a front view of the magnetic control oil-water separation device.
FIG. 3: an exemplary distillation unit process flow diagram.
FIG. 4: schematic diagram of an exemplary biochemical processing unit.
FIG. 5: schematic diagram of an exemplary ozone catalytic oxidation unit.
Description of the reference numerals
In fig. 2:
1. a separator; 101. a water tank; 102. a drive motor; 103. a magnetic turntable; 104. mounting grooves; 105. a fixed shaft; 106. a squeegee; 107. a fixing plate; 108. an extension spring; 109. a collection canister; 2. a mixer; 21. a mixing box; 22. a water inlet pipe; 3. a magnetic Janus particle disperser; 4. a recoverer; 41. a recycling bin; 42. sludge calandria; 5. a sewage inlet pipe; 6. a vertical tube; 7. a first conduit; 8. a second conduit; 9. a dirt blocking cover; 10. a moving magnet; 11. a fixed magnet; 12. a transparent glass plate; 13. a blow-off pipe; 14. and (7) covering the tube.
In fig. 3:
1-1: a water inlet; 1-2: grid forming; 1-3: a lift pump; 2-1: a water inlet weir; 2-2: an aeration device; 2-3: a reflux weir crest; 2-4: an effluent weir; 2-5: biological fillers; 3-1: water outlet
Detailed Description
In the present specification, the meaning of "may" or "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, the unit names used are all international standard unit names, and "%" used means weight or mass% content, if not specifically stated.
The "organic pollutant-containing wastewater" or "organic matter-containing wastewater" in the present specification refers to wastewater containing organic pollutants, and is sometimes referred to as "organic solvent-containing wastewater", which is mainly derived from sewage containing organic solvent components, wherein a part of the organic solvent exists in the form of an oil phase, and another part exists in a dissolved form. Among them, organic pollutants in the form of oil phase, which may also be referred to as "water-insoluble organic matter", include organic matter immiscible with water, such as oil slick, emulsified oil, and solid oil. The organic substance present in a dissolved form, which may also be referred to as "dissolved form organic substance", includes organic substances having a certain solubility in water, including, for example, methanol, ethanol, N-propanol, isopropanol, ethylene glycol, propylene glycol, glycerol, acetone, tetrahydrofuran, N-isopropylacrylamide, diethyl ether, dimethyl ether, acetic acid, and the like, and also includes organic substances having a low solubility in water or being insoluble in water but being miscible with the above-mentioned organic substances having a certain solubility in water, such as toluene, xylene, and the like.
In the present specification, the "magnetic Janus particles" refer to amphiphilic particles capable of responding to a magnetic field, and the kind thereof is not particularly limited as long as they have magnetism and amphiphilic properties and can function as a solid emulsifier. For example, amphiphilic magnetic organic/inorganic composite particles, and the like. The magnetic Janus particles may have an average particle size of 10-2000nm.
In the present specification, the "magnetic Janus particle emulsion" refers to an emulsion obtained by dispersing and emulsifying magnetic Janus particles as a solid emulsifier in a target treatment liquid, in which the magnetic Janus particles are dispersed in an aqueous phase as a continuous phase while forming a dispersed phase by coating oil droplets with the magnetic Janus particles.
The target treatment liquid comprises wastewater containing organic pollutants, particularly wastewater containing high-concentration organic solvent pollutants. For example, the COD value of the high-concentration COD organic solvent wastewater is about 250000-300000ppm.
The COD refers to chemical oxygen demand and is an important index for representing organic pollution of water. The method is characterized in that the amount of reducing substances needing to be oxidized in a water sample is measured by a chemical method, and the reducing substances in the wastewater mainly comprise organic matters. The larger the COD value is, the more serious the water body is polluted by the organic matters.
The high-concentration COD organic solvent wastewater is derived from pharmaceutical wastewater, chemical fertilizer wastewater, textile printing and dyeing wastewater, dye wastewater, tanning wastewater, pesticide wastewater and the like. The amount of the magnetic Janus particles relative to the target treatment fluid can be determined and adjusted according to the pollution degree and the oil content of the target treatment fluid, and can be 0.01-20wt% for example.
The invention provides a method for treating wastewater containing organic pollutants, which comprises the following steps:
step 1: mixing magnetic Janus particles in waste water containing organic pollutants to obtain emulsion, and enabling emulsion droplets of the magnetic Janus particles serving as dispersed phases in the emulsion to migrate and/or be enriched under the action of a magnetic field, so that water-insoluble organic matters are separated from the waste water, and discharging a treatment solution 1;
step 2: distilling the treatment solution 1, separating and recovering part of dissolved organic matters, and discharging a treatment solution 2;
and 3, step 3: performing biochemical treatment on the treatment solution 2, degrading partial dissolved organic matters by using microorganisms, and discharging the treatment solution 3;
and 4, step 4: the treatment liquid 3 was subjected to catalytic ozonation.
In one embodiment, the step 1 comprises: forming magnetic Janus particles into an aqueous dispersion with the solid content of 1-20wt%, and mixing the aqueous dispersion with the wastewater to obtain a stable oil-in-water emulsion, wherein magnetic Janus particle emulsion droplets formed by coating water-insoluble organic matters on the magnetic Janus particles are used as a dispersion phase; using a magnet to cause migration and/or enrichment of the magnetic Janus particle emulsion droplets onto or near the magnet; the continuous phase is discharged.
One part of the dissolved organic solvent in the continuous phase can be separated by distillation, and the other part of the dissolved organic pollutant which is difficult to separate by distillation is further removed by microbial degradation and catalytic oxidative degradation.
The steps 1-4 can be respectively implemented in an oil-water separation unit, a distillation unit, a biochemical treatment unit and an ozone catalytic oxidation unit.
An oil-water separation unit:
in the oil-water separation unit, the magnetic Janus particles and the magnetic field are used for separating water-insoluble organic matters from the wastewater. Specifically, magnetic Janus particles are formed into an aqueous dispersion with the solid content of 1wt% -20wt%, the aqueous dispersion is mixed with the wastewater, and a stable oil-in-water emulsion is obtained through proper shearing action, wherein magnetic Janus particle emulsion droplets formed by coating water-insoluble organic matters on the magnetic Janus particles are used as a dispersed phase; separating water insoluble organic matter by allowing the magnetic Janus particle emulsion droplets to migrate and/or concentrate on or near the magnet under the action of a magnetic field generated by the magnet; the continuous phase containing the organic matter in dissolved form is discharged. The continuous phase is taken as a treatment liquid 1 to enter a distillation unit for subsequent distillation treatment.
The oil-water separation unit comprises a magnetic control oil-water separation device capable of realizing the scheme. The device comprises a container capable of containing waste water; and a magnet configured to generate a magnetic force on the magnetic Janus particle emulsion droplet within the container.
The magnetic Janus particles used in the present invention are not particularly limited, but Janus particles having magnetic properties and amphiphilic properties and being usable as a solid emulsifier may be used, and NH is preferable 2 -Fe 3 O 4 -C 8 。
NH 2 -Fe 3 O 4 -C 8 Fe in the particles 3 O 4 Having magnetic properties, fe 3 O 4 The surface of the particle is provided with a silicon oxide shell layer, and a part of the surface of the particle is provided with amino (-NH) 2 ) I.e. the hydrophilic part, and a part with a C8 group, i.e. the hydrophobic part obtained by modification with n-octyltriethoxysilane.
NH 2 -Fe 3 O 4 -C 8 The following method can be used for preparation. Using 1g of Fe with a particle size in the range of 100-200nm 3 O 4 The nano-particles are used as carrier particles; using 0.01-0.2g of ethyl orthosilicate in Fe 3 O 4 Preparing a silica shell layer with the thickness of 5-50nm on the surface of the nano-particles through a sol-gel process to obtain composite magnetic nano-particles; the composite magnetic nanoparticles are used as a particle emulsifier, 50g of water and 10g of paraffin are emulsified at the temperature of 60 ℃ to obtain a stable oil-in-water emulsion, the stable solid paraffin droplets are obtained after the stable solid paraffin droplets are cooled to room temperature, the particles are embedded into an oil-water interface, one side of the stable solid paraffin droplets is exposed in a water phase, and the other side of the stable solid paraffin droplets is embedded into Dan Laxiang; the paraffin wax droplets obtained above were dispersed in 10g of dimethyl sulfoxide DMSO solvent, and aminopropyltriethoxysilane (added in an amount of Fe) 3 O 4 1-10% of the mass of the nano particles) and the surface grafting modification of the silane coupling agent can be realized within 1 hour through a simple stirring process. Further, the solid paraffin droplets were separated by centrifugation, dissolved in 10g of ethanol solvent, and centrifuged again to obtain magnetic particles with one side amino group modified. The amino-modified magnetic particles were redispersed in 10g of ethanol and n-octyltriethoxysilane (added in an amount of Fe) 3 O 4 1% -10% of the mass of the nano particles) to obtain hydrophobic part modification on the other side again. Magnetic Janus particles were finally obtained.
The magnet used in the present invention is not particularly limited, and may be any magnet that is conventional in the art, and examples thereof include samarium cobalt magnets, neodymium iron boron magnets, ferrite magnets, alnico magnets, iron chromium cobalt magnets, and the like. The magnet is configured to produce a magnetic field in the container or processing chamber having a magnetic induction in the range of 500-25000 gauss (Gs). The shape of the magnet is not particularly limited as long as it can fit into the treatment chamber, and may be, for example, a plate shape, a block shape, a columnar shape, or the like.
In one embodiment of the present invention, a magnetic control oil-water separation device includes: the water tank, water inlet, delivery port, oil-out, scraper blade, support dwang, magnet, motor, follow driving wheel, driving belt etc. constitute. The magnetic control oil-water separation equipment has power of 0.5-1.0kw, operation temperature is not particularly limited, and the equipment can be operated in the range of 1-100 deg.C, and flow rate can be 0.5m 3 -2.5m 3 /h。
In a specific scheme, the specific operation process and process in the oil-water separation unit are as follows: mixing the aqueous dispersion (with the solid content of 1-20 wt%) of the magnetic Janus particles with the wastewater containing organic pollutants to be treated, and obtaining a stable oil-in-water emulsion through shearing action; the oil-in-water emulsion flows into a water tank through a water inlet, and a magnet is partially immersed in water flow and pulls and adsorbs the emulsion stabilized by the magnetic particles through magnetic control; the motor rotates to drive the transmission belt, so that the driven wheel is driven to rotate, the support rotating rod is driven, and the support rotating rod is connected with the magnet, so that the magnet rotates; the magnet rotates to drive the magnetic Janus particle emulsion drops adsorbed on the surface of the magnet to leave the water flow; under the action of the scraper, the magnetic particles on the magnet and the stable oil phase liquid drops thereof are separated from the magnet; the solvent sewage after the oil phase is separated is discharged through a water outlet, so that the oil-water separation is realized.
In a specific scheme, the oil-water separation unit adopts an oil-water separation device shown in FIG. 2. The oil-water separation device is provided with a separator, a mixer, a magnetic Janus particle disperser, a recoverer and the like.
The magnetic Janus particles are added to a magnetic Janus particle disperser 3 for dispersion, and then the magnetic Janus particle dispersion is introduced into a mixer 2 through a standpipe 6 to be mixed with the sewage water to form an emulsion. The magnetic Janus particles are mixed with the oily sewage and then are enriched at an oil-water interface, and the oil phase is wrapped to form magnetic Janus particle emulsion droplets. The emulsion separates in getting into separator 1 through advancing dirty pipe 5, control driving motor 102 operation, and driving motor 102's output shaft drives magnetism carousel 103 and rotates, and magnetism Janus granule emulsion drops adsorbs on magnetism carousel 103 to can make greasy dirt and sewage separation. Under the action of the extension spring 108, the scraper 106 can be tightly attached to the outer edge of the magnetic rotary disc 103, so that magnetic Janus particles on the magnetic rotary disc 103 can be scraped, the magnetic Janus particles and the coated oil phase enter the collecting cylinder 109 along the scraper 106 and enter the recoverer 4 through the first conduit 7, the recoverer 4 separates oil stains and the magnetic Janus particles, and the recovered magnetic Janus particles are conveyed to the mixer 2 for recycling.
A distillation unit:
the distillation unit is used to separate the partially dissolved form of the organic matter contained in the wastewater, and a conventional distillation apparatus in the art may be used as long as the above-mentioned object can be achieved.
In one embodiment, the distillation treatment apparatus is used at a treatment capacity of 60t/d, and the treated wastewater contains a portion of the solvent in a dissolved form which is not efficiently separated by the oil-water separation unit (the component is a low boiling point component which has a lower boiling point than the main target product and is azeotropic with water, and the composition thereof is not determined depending on the kind or source of the wastewater).
Useful components (such as organic solvents such as methanol and ethanol and available component mixtures) in the wastewater can be purified and separated by a distillation unit, and the main processes comprise rectification and condensation to obtain a part of useful mixed solvent.
In one specific scheme, the production process flow is as follows: for the wastewater subjected to the oil-water separation treatment, the COD data was confirmed. And collecting the wastewater to be treated, putting the wastewater into an intermediate storage tank for later use, pumping the wastewater to be treated into a rectifying tower by using a diaphragm pump during production, and then heating and rectifying the wastewater in the rectifying tower step by step according to the boiling point of each target product.
Preferably, the four distillations are performed according to the boiling point of the target product, the first distillation temperature is set to 75 ℃, the fractional distillation is such as methanol, ethanol, etc., the second distillation temperature is set to 90 ℃, the fractional distillation is such as toluene, xylene, etc., the third distillation temperature is set to 100 ℃, the main fractional water, and the fourth distillation temperature is set to, for example, 200 ℃ to fractionate the mid-boiling components.
In one embodiment, first, the distillation column is heated with jacket steam to perform a first distillation at a temperature of 75 ℃, low boiling point substances are evaporated from wastewater to be treated, condensed in a condenser and indirectly condensed with cooling water (the condensation method is indirect condensation, water is used as a refrigerant, and a cooling medium is tap water), and products (for example, mainly methanol, ethanol, etc.) are fractionated. After the above operation is completed, the remaining wastewater to be treated in the rectifying tower is subjected to a second heating distillation at 90 ℃, and a substance azeotropic with water is evaporated from the wastewater to be treated, condensed in a condenser, and a product (for example, mainly toluene, xylene, etc.) is fractionated. And after the operation is finished, carrying out third heating distillation on the residual wastewater in the rectifying tower, setting the temperature to be 100 ℃, evaporating water from the wastewater, condensing in a condenser, and fractionating to obtain a product (mainly water). And finally, carrying out fourth heating distillation on the residual kettle liquid in the rectifying tower, regulating the temperature to 200 ℃, evaporating the medium boiling point components in the residual liquid, condensing by a condenser, and taking the residual kettle liquid as a byproduct for sale. The distillation residue is discharged and then used as a treatment liquid 2 for the next biochemical treatment.
The device can comprise one set of rectifying tower and two sets of condensing devices which are correspondingly configured, wherein the condensing effect is achieved by indirect condensation of cooling water in a condenser, waste gas reaches the top of the tower through a plurality of sections of tower sections in the condensation process, the height of the rectifying tower (comprising rectifying facilities and the condensing devices) is 15m, and the area of the condenser is 80m 2 The mass transfer and heat transfer of the condensation process are sufficient, the condensation efficiency is high, the temperature in the accurate regulating tower ensures the effective separation of possibly existing azeotrope, a small amount of extractant can be added when necessary to ensure the separation efficiency, the extractant is pumped into the distillation still from an inlet pipeline, and according to actual conditions, the extractant can be recycled for multiple times after condensation.
A biochemical treatment unit:
after the wastewater is treated by the two units, most organic matters are separated and recovered, but part of water-soluble organic matters remain in the wastewater and are difficult to separate. And the biochemical treatment unit is used for performing biochemical treatment on the treatment liquid obtained in the previous step and degrading the partially dissolved organic matters in the wastewater by using microorganisms.
The biochemical treatment unit may employ a device conventional in the art as long as the above-mentioned object can be achieved.
In a specific scheme, the sewage biochemical treatment unit comprises an anoxic tank, an aerobic tank and a sedimentation tank. A water inlet, a lift pump and a grid are arranged in the anoxic tank; the aerobic tank is internally provided with a water inlet weir, an aeration device, a reflux device, a water outlet weir and a biological filler; the outer wall of the sedimentation tank is provided with a water outlet. The treatment capacity of the sewage biochemical treatment equipment is 5m 3 The temperature range of the anoxic pond is 5-25 ℃, and the pH value is 6.5-7.5; the temperature of the aerobic tank is 10-35 ℃, and the pH value is 7.5-8.5. The power of the device is 5-10kW. In the present invention, conventional strains may be used in the anoxic tank and the aerobic tank. In one embodiment, denitrifying bacteria, such as Pseudomonas bacteria, are used in the anoxic tank; nitrite bacteria, such as pediococcus, nitrate bacteria, such as Proteus, and polyphosphate bacteria, such as Proteus, are used in the aerobic tank, for example, in an amount of 10mg/L.
BOD may be used in the process unit 5 As an evaluation index. BOD 5 Is five-day biochemical oxygen demand, is an index for indirectly representing the degree of water body polluted by organic matters by using dissolved oxygen consumed by microbial metabolism, and can reflect the degree of wastewater polluted by organic matters, and the more organic matters contained in the wastewater, the more oxygen is consumed, and BOD 5 The higher the value and vice versa.
In one embodiment, the biochemical treatment process of the wastewater comprises the following steps: the wastewater to be treated enters from the water inlet, and the large particle suspended solids are filtered by the grid and then enter the anoxic tank. The anoxic tank is an anoxic and weakly alkaline environment. The denitrifying bacteria utilize organic matters in the sewage as carbon source to carry a great amount of NO into the reflux liquid of the aerobic tank 3 -N and NO 2 Reduction of-N to N by denitrification 2 Released to the air, thus BOD 5 Decrease in concentration, NO 3 The concentration of-N is greatly reduced. The sewage in the anoxic tank is uniformly distributed to the aerobic tank through the water inlet weir by the lifting pump. The sewage is aerobically biodegraded in an aerobic tank, and organic matters are biochemically degraded by microorganisms under aerobic conditions, namely BOD 5 The concentration continues to decrease; NH is generated by the action of nitrite bacteria and nitrate bacteria 3 Oxidation of-N to NO 3 -N and NO 2 N, to NH 3 The N concentration drops significantly, but NO is produced as a result of the nitration process 3 -N and NO 2 -an increase in the concentration of N; phosphorus also declines at a faster rate under the action of phosphorus accumulating bacteria. Microorganisms capable of accumulating phosphorus in the activated sludge in the aerobic tank can absorb a large amount of soluble phosphorus, convert the soluble phosphorus into insoluble poly-orthophosphate and store the insoluble poly-orthophosphate in vivo, and finally discharge the residual sludge through a sedimentation tank to achieve the aim of removing phosphorus in the system. The process has the functions of organic matter removal, nitrification, phosphorus removal and the like.
Organic matters which are difficult to be degraded by microorganisms and are in a dissolved form may be contained in the wastewater treated by the biochemical treatment unit, namely the discharged liquid after the organic matters in a partially dissolved form are degraded by the microorganisms, and the wastewater is taken as the treatment liquid 3 and introduced into a subsequent ozone catalytic oxidation unit for subsequent treatment.
An ozone catalytic oxidation unit:
the treatment liquid obtained from the former unit treatment may contain organic matters which are in dissolved form and difficult to be degraded by microorganisms, and the wastewater is subjected to ozone catalytic oxidation to remove the organic matters.
In one embodiment of the invention, the ozone catalytic oxidation unit mainly comprises a control cabinet, a circulating water storage tank, a three-section type aeration tower, an ozone generator and the like. Wherein the three-section aeration tower is loaded with catalyst.
After the treatment by the operation process, the COD value of the high-concentration COD organic solvent oily sewage is greatly reduced, but part of the persistent organic pollutants still remain. The wastewater discharged after the three units is treated is introduced into an ozone catalytic oxidation device, the flow rate is 0.5-2.0 tons/hour, the wastewater is circularly treated, and the treatment time of a single ton grade is 2-4 hours. Controlled by a control cabinetAnd (4) process parameters, namely injecting the wastewater into a circulating reservoir and pumping the wastewater into a three-section aeration tower. The capacity of the aeration tower is 0.5 ton, and Co-Mn/ZrO is loaded 2 A catalyst.
Ozone is generated by an ozone generating device, the ozone generating amount is 200g/h, and the ozone is introduced into the device to realize the catalytic oxidation process. The COD of the wastewater treated by the process is greatly reduced.
The invention relates to a treatment device for wastewater containing organic pollutants, which comprises an oil-water separation unit, a water separation unit and a water separation unit, wherein the oil-water separation unit is connected in sequence; a distillation unit for separating partially dissolved form organics in the wastewater; a biochemical treatment unit for degrading a portion of the dissolved form of the organic matter; the ozone catalytic oxidation unit is used for catalytically oxidizing dissolved and non-degradable organic matters, so that continuous gradual separation or removal of different organic pollutants contained in the wastewater can be realized. The COD value of the high-concentration COD organic solvent wastewater can be reduced from about 250000-300000ppm to about 200ppm by the treatment of the treatment equipment. The technical solution claimed by the present invention is explained below by specific examples.
The COD value of the wastewater is tested by the following method:
10.00mL of water sample is taken, pure water is added to 20.00mL, potassium dichromate with different concentrations (0.25, 0.025 mol/L) is used for oxidation, and the rest steps are carried out according to the operation method in HJ-T-70-2001.
The COD value of the oily high-concentration COD organic solvent wastewater used in example 1 was 250000ppm and its source was pharmaceutical wastewater.
The COD value of the oily high-concentration COD organic solvent wastewater used in example 2 was 200000ppm and the source thereof was pharmaceutical wastewater.
Preparation example: NH 2 -Fe 3 O 4 -C 8 Preparation of granules
Using 1g of Fe with a particle size in the range of 100-200nm 3 O 4 The nano-particles are used as carrier particles; using 0.01-0.2g of ethyl orthosilicate in Fe 3 O 4 Preparing a silica shell layer with the thickness of 5-50nm on the surface of the nano-particles through a sol-gel process to obtain composite magnetic nano-particles; by using the aboveThe composite magnetic nano-particles are used as particle emulsifying agents, stable oil-in-water emulsion is obtained by emulsifying 50g of water and 10g of paraffin at the temperature of 60 ℃, stable solid paraffin droplets are obtained after the stable oil-in-water emulsion is cooled to room temperature, the particles are embedded into an oil-water interface, one side of the particles is exposed in a water phase, and the other side of the particles is embedded into Dan Laxiang; the paraffin wax droplets obtained above were dispersed in 10g of dimethyl sulfoxide DMSO solvent, and aminopropyltriethoxysilane (added in an amount of Fe) 3 O 4 1-10% of the mass of the nano particles) and the surface grafting modification of the silane coupling agent can be realized within 1 hour through a simple stirring process. Further, the solid paraffin droplets were separated by centrifugation, dissolved in 10g of ethanol solvent, and centrifuged again to obtain magnetic particles with one side amino group modified. The amino-modified magnetic particles were redispersed in 10g of ethanol and n-octyltriethoxysilane (added in an amount of Fe) 3 O 4 1% -10% of the mass of the nanoparticles) can be modified to obtain another side hydrophobic part modification again. Finally obtaining the magnetic Janus particle NH 2 -Fe 3 O 4 -C 8 。
Example 1:
aiming at the oily high-concentration COD organic solvent wastewater, 1kg of magnetic Janus particles are dispersed in a water system through an ultrasonic dispersion system to obtain a dispersion liquid. The magnetic Janus particle dispersion liquid is mixed with high-concentration COD oily organic solvent wastewater with a COD value of 250000, the dosage of the magnetic Janus particles relative to the wastewater is 1wt%, stable emulsification is realized under the action of strong mechanical stirring, and the oil phase solvent is emulsified to obtain dispersed phase oil drops. The oil drops stabilized by the magnetic Janus particles are separated under the treatment of magnetic separation equipment, so that the separation of an oil phase solvent and a water phase in a system is realized.
The organic solvent waste water after the oil phase solvent separation still contains part of the dissolved organic solvent, but the COD value of the organic solvent waste water is greatly reduced to 150000. The waste water thus discharged is further pumped into a distillation apparatus, from which a large amount of solvent in dissolved form can be separated and recovered. First, the distillation column is heated with jacket steam to perform a first distillation at a temperature of 75 ℃, low boiling substances are distilled from high concentration wastewater, and the low boiling substances are indirectly condensed with cooling water in a condenser (the condensation method is indirect condensation, water is used as a refrigerant, and a cooling medium is tap water), and products (mainly methanol, ethanol and the like) are fractionated, so that the COD can be reduced from 150000 to about 100000. After the operation is finished, the residual waste liquid in the rectifying tower is heated and distilled for the second time, the temperature is set to be 90 ℃, substances which are azeotroped with water are evaporated from the waste liquid, the substances are condensed in a condenser, and products (mainly toluene, xylene and the like) are fractionated, so that the COD of the waste liquid can be reduced from 100000 to about 30000. After the above operation is finished, the remaining waste liquid in the rectifying tower is heated and distilled for the third time, the temperature is set to be 100 ℃, water is evaporated from the waste liquid, the water is condensed in a condenser, and a product (mainly water) is fractionated. And finally, carrying out fourth heating distillation on the residual kettle liquid in the rectifying tower, regulating the temperature to 200 ℃, evaporating the medium boiling point components in the residual liquid, condensing by a condenser, and selling as a byproduct. The COD of the residual liquid in the tower bottom is basically about 20000.
Then pumping the discharged liquid into the next working unit, wherein the biochemical treatment device firstly passes through an anoxic tank, the temperature range is 5-25 ℃, and the pH value is 6.5-7.5; then the sewage passes through an aerobic tank with the temperature range of 10-35 ℃ and the pH value of 7.5-8.5, and finally enters a sedimentation tank. The strain is selected from Proteus, pseudomonas and Micrococcus. Wherein, the pseudomonas is positioned in the anoxic tank, the proteus and the pediococcus are positioned in the aerobic tank. The COD of the waste liquid is further reduced to 5000 by the biochemical treatment device. The discharged liquid is subjected to serial oil-water separation, dissolved organic solvent recovery and biochemical treatment, most of COD can be removed by separation recovery and biochemical degradation, and a small part of dissolved organic solvent which is difficult to degrade is remained. And further pumping the discharged liquid into an ozone catalytic oxidation device to remove the organic matter in the residual dissolved form. The treatment flow rate of the ozone catalytic oxidation device is 1t/h, the circulating treatment capacity is 1t/h, the mass of ozone consumption is 250g, and Co-Mn/ZrO is used 2 A catalyst. Through the whole set of series of treatment processes, the COD value is reduced to about 200, and the standard emission is met.
Example 2:
aiming at the oily high-concentration COD organic solvent wastewater, 1kg of magnetic Janus particles are dispersed in a water system through an ultrasonic dispersion system to obtain a dispersion liquid. The magnetic Janus particle dispersion liquid is mixed with high-concentration COD oily organic solvent wastewater with a COD value of 200000, the dosage of the magnetic Janus particles relative to the wastewater is 1wt%, stable emulsification is realized under the action of strong mechanical stirring, and the emulsification of the oil phase solvent is realized to obtain dispersed phase oil drops with stable magnetic Janus particles. Oil drops stabilized by the magnetic Janus particles are enriched on the magnet under the treatment of the magnetic separation equipment, so that the separation of an oil phase solvent and a water phase in a system is realized. The organic solvent waste water after the oil phase solvent separation still contains part of soluble organic solvent, but the COD value is greatly reduced to 100000.
Further pumping the discharged wastewater into a distillation device, separating and recovering a large amount of soluble solvent through a distillation process, and reducing the COD value of the discharged liquid of the section to 30000. Then the discharged liquid is continuously pumped into the next working unit, and the COD is further reduced to 3000 by the biochemical treatment device. The discharged liquid is subjected to serial oil-water separation, dissolved organic solvent recovery and biochemical treatment, most COD is removed in a separation recovery and biochemical degradation mode, and a small part of soluble difficultly-degraded COD still remains. And the discharged liquid is further pumped into an ozone catalytic oxidation device, so that the partial removal of the residual dissolved COD can be realized. The treatment flow rate of the ozone catalytic oxidation device is 1t/h, the circulating treatment capacity is 1t/h, the mass of ozone consumption is 200g, and Co-Mn/ZrO is used 2 A catalyst. Through the whole set of series of treatment processes, the COD value is reduced to about 200, and the standard emission is met.
Claims (10)
1. A method for treating wastewater containing organic pollutants, which is characterized by comprising the following steps:
step 1: mixing magnetic Janus particles in waste water containing organic pollutants to obtain emulsion, and enabling emulsion droplets of the magnetic Janus particles serving as a dispersion phase in the emulsion to migrate and/or enrich under the action of a magnetic field, so that water-insoluble organic matters are separated from the waste water, and discharging a treatment solution 1;
step 2: distilling the treatment solution 1, separating and recovering part of dissolved organic matters, and discharging the treatment solution 2;
and step 3: performing biochemical treatment on the treatment solution 2, degrading partial dissolved organic matters by using microorganisms, and discharging the treatment solution 3;
and 4, step 4: the treatment liquid 3 was subjected to catalytic ozonation.
2. The processing method according to claim 1,
the step 1 comprises the following steps: forming magnetic Janus particles into an aqueous dispersion with the solid content of 1-20wt%, and mixing the aqueous dispersion with the wastewater to obtain a stable oil-in-water emulsion, wherein magnetic Janus particle emulsion droplets formed by coating water-insoluble organic matters on the magnetic Janus particles are used as a dispersion phase; using a magnet to cause migration and/or enrichment of the magnetic Janus particle emulsion droplets onto or near the magnet; discharging the continuous phase;
the dosage of the magnetic Janus particles relative to the wastewater containing organic pollutants is 0.01-20wt%.
3. The processing method according to claim 1 or 2,
the magnetic Janus particle is NH 2 -Fe 3 O 4 -C 8 And (3) granules.
4. The processing method according to any one of claims 1 to 3,
the catalyst adopted in the step 4 is selected from Co-Mn/ZrO 2 A catalyst.
5. An apparatus for treating wastewater containing organic pollutants, comprising:
an oil-water separation unit: separating water-insoluble organic matters from the wastewater by using magnetic Janus particles and the action of a magnetic field;
a distillation unit: for separating partially dissolved form organics in the wastewater;
a biochemical treatment unit: for degrading partially dissolved form organic matter;
an ozone catalytic oxidation unit: used for catalytic oxidation of dissolved and refractory organics.
6. The processing apparatus according to claim 5,
in the oil-water separation unit, magnetic Janus particle emulsion droplets are migrated and/or enriched through the action of a magnetic field so as to separate water-insoluble organic matters;
the magnetic Janus particle emulsion droplets are dispersed phases formed by coating water-insoluble organic matters on magnetic Janus particles in emulsion obtained by emulsifying the wastewater by using the magnetic Janus particles as a solid emulsifier.
7. The processing apparatus according to claim 6,
the oil-water separation unit comprises a magnetic control oil-water separation device, and the magnetic control oil-water separation device comprises a container capable of containing wastewater; and
a magnet configured to generate a magnetic force on the magnetic Janus particle emulsion droplet within the container.
8. The processing apparatus according to any one of claims 5 to 7,
the magnet is fixedly configured or configured to be movable or rotatable.
9. The processing apparatus according to any one of claims 5 to 8,
the distillation unit includes a rectification column and a condenser.
The biochemical treatment unit comprises an anoxic tank, an aerobic tank and a sedimentation tank; a water inlet, a lift pump and a grid are arranged in the anoxic tank; the aerobic tank is internally provided with a water inlet weir, an aeration device, a reflux device, a water outlet weir and a biological filler;
the ozone catalytic oxidation unit comprises a control cabinet, a circulating water storage tank, a three-section aeration tower and an ozone generator, wherein a catalyst is loaded in the three-section aeration tower.
10. A method for treating wastewater containing organic contaminants using the treatment apparatus of any one of claims 5-9, comprising:
a step of separating water-insoluble organic substances from the wastewater by using magnetic Janus particles and the action of a magnetic field;
a step of distilling the treatment liquid obtained in the previous step to separate and recover a part of dissolved organic matters in the wastewater;
performing biochemical treatment on the treatment liquid obtained in the previous step, and degrading partial dissolved organic matters in the wastewater by using microorganisms;
and (3) carrying out catalytic ozonation on the treatment liquid obtained in the previous step to oxidize dissolved and difficultly degraded organic matters in the wastewater.
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| CN115105861A (en) * | 2021-03-18 | 2022-09-27 | 清华大学 | Oil-water separation method based on magnetic solid particle emulsifier |
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