CN110204031A - The integrated apparatus and its application method of light Fenton-just infiltration Combined Treatment bio-refractory organic wastewater - Google Patents
The integrated apparatus and its application method of light Fenton-just infiltration Combined Treatment bio-refractory organic wastewater Download PDFInfo
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- CN110204031A CN110204031A CN201910485426.3A CN201910485426A CN110204031A CN 110204031 A CN110204031 A CN 110204031A CN 201910485426 A CN201910485426 A CN 201910485426A CN 110204031 A CN110204031 A CN 110204031A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The present invention relates to the integrated apparatus and its application method of a kind of smooth Fenton-just infiltration Combined Treatment bio-refractory organic wastewater, which includes light Fenton unit and the positive permeation unit of immersion.It the use of the method that the device carries out water process include light Fenton process and positive process of osmosis, while effectively degrading using light Fenton processing unit or convert organic pollutant, using the retention light Fenton process degradation of forward osmosis membrane selective penetrated property or convert incomplete organic pollutant, the positive permeation unit of immersion uses the positive infiltration structure of immersion, without water inlet end circulating pump and water inlet tank body, compact overall structure, low energy consumption, easily combines with other techniques or device.The active material that light Fenton unit generates is converted in contaminant degradation and is exhausted into positive permeation unit transition process, and strong oxidizing property will not influence the stability of film, and wastewater treatment rate is high, effect is good, is suitable for promoting the use of.
Description
Technical field
The invention belongs to field of waste water treatment, are related to wastewater biological degradation further treatment technique, especially a kind of smooth Fenton-
The integrated apparatus and its application method of positive infiltration Combined Treatment bio-refractory organic wastewater.
Background technique
With modern industry and the high speed development of related industry, pollutant kind increases year by year in industrial wastewater, causes work
The features such as complicated component, pollutional load are high, risk of toxicity is big is presented in industry waste water.Existing technique for treating industrial wastewater is frequently with good
The microbial process that oxygen-anaerobism combines removes removal organic polluter to achieve the purpose that reduce COD, however, due to some difficult to degrade
The genotoxic potential and bio-refractory (BOD of organic pollutant5/ COD < 0.4), microbial method (including membrane bioreactor
MBR the degradation and conversion that) cannot effectively realize organic pollutant, eventually lead to organic pollutant and accumulate in waste water, are discharged nothing
Method meets qualified discharge requirement, threatens to ecological environment.The conventional pressures such as nanofiltration, reverse osmosis membrane technology companion when producing water purification
Raw a large amount of high concentrated organic wastewaters, need to be further processed, and membrane pollution problem is also the technology pain for restricting membrane process and promoting and applying
Point and difficult point；There are adsorbent reactivation, recycling etc. to handle handling problems for absorption method.
Above-mentioned physics and biological treatment are compared, as important branch in chemical method water treatment technology, with Fenton
(Fenton) technique is the high-level oxidation technology of representative, Fenton reagent (H2O2And Fe2+) generate Strong oxdiative active material without
Degradation selectivity even permineralization organic pollutant, is effectively improved wastewater biodegradability, improves effluent quality and waste water recycling
Rate.But tradition Fenton technique requires harsh, H in treatment process to inlet flow-patterm2O2Usage amount is big, is also easy to produce iron cement.It is derivative
The shortcomings that light-Fenton technology overcomes traditional Fenton has reaction condition mild, H2O2Usage amount is low, does not generate secondary pollution
The advantages that, potential prospects for commercial application is shown in high-concentration biological organic wastewater with difficult degradation thereby field.
A kind of smooth Fenton catalysis oxidation coal chemical industrial waste water advanced treatment apparatus of patent of invention (CN105236510A) and its make
With method, since coal chemical industrial waste water contains the poisonous and harmful substances such as a large amount of phenols, polycyclc aromatic compound and cyanogen, oil, ammonia nitrogen,
Easily pollute the environment.The device is up to 95% or more to COD in coal chemical industrial waste water and ammonia nitrogen removal frank, but does not refer to useless
Dissolubility salinity in water, such as the removal efficiency of CN- plasma；Process using the immobilized active carbon of prussian blue as catalyst,
Heterogeneous fenton catalyst is related to the post-processings problem such as recycling；The ultraviolet lamp source service life used is short, and permeability is poor in waste water, shadow
Acoustic system operational efficiency and stability；Ultraviolet lamp source fever is serious, and the temperature control system matched is added to increase the complexity and energy of device
Consumption.
A kind of light Fenton reactor for handling organic wastewater with difficult degradation thereby of patent of invention (CN207210048U), though the reactor
It uses UV LED for light source, overcomes traditional UV lamps shortcomings used in light Fenton process, but react
Device is with FeSO4For homogeneous light fenton catalyst, Fe in wastewater treatment process2+Easily it is oxidized and reaction is entered by middle part diversion pipe
It is discharged chamber above device, homogeneous catalyst will be caused to be lost if do not increased subsequent processing units, and finally influence effluent quality.
A kind of ultraviolet-aided heterogeneous Fenton oxidation sewage water treatment method of patent of invention (CN104445571A), light Fenton are urged
Agent is the solid-supported catalyst film with mesopore orbit, though configuration solves the problems, such as heterogeneous fenton catalyst recycling, model
It is more than 90% to low concentration decoloring dye waste water rate, but membrane type catalyst is effectively catalyzed area and processing water is limited, installation is expanded
It opens up and difficult in maintenance, anti-current-rush ability is weak.Device uses traditional UV sources, easily causes foregoing invention patent
The problems in CN105236510A.
Positive process of osmosis is the membrane process that spontaneous progress is driven with permeable pressure head, does not need additional motive power, is produced needed for water
Low energy consumption, layer of contaminants short texture on the outside of film, alleviate in conventional pressure membrane process because caused by high drive film surface it is dirty
Contaminate layer densification problem, the processing with other combine processes for (dirt) water that gives up of positive process of osmosis.But independent positive process of osmosis
In retained due to the selectivity of film, pollutant concentration continuous improvement is also easy to produce outer concentration polarization phenomenon on the outside of film, influences to produce water effect
Rate, and the high concentration organic contaminant waste water of water inlet end need to be further processed disposition after positive process of osmosis.
Summary of the invention
It is an object of the invention to overcome, single smooth Fenton, forward osmosis membrane process and device processing biology are difficult in the prior art
The defect of degradation of organic waste water, takes into account that bio-refractory treatment of Organic Wastewater difficulty is big and its potential hazard to ecological environment,
There is provided it is a kind of for bio-refractory organic wastewater integrated apparatus and its application method, in conjunction with light Fenton and positive infiltration technology,
Influent COD can be effectively reduced simultaneously producing water purification in light Fenton technology, improve wastewater biodegradability, the selection for being aided with forward osmosis membrane is saturating
The property crossed, further promotes effluent quality, effectively solves existing bio-refractory organic wastewater process efficiency, film concentration polarization
And the problems such as pollution.
The present invention solves its technical problem and adopts the following technical solutions to achieve:
A kind of smooth Fenton-is just permeating the integrated apparatus of Combined Treatment bio-refractory organic wastewater, including light Fenton list
Member and the positive permeation unit of immersion, light Fenton unit connect the positive permeation unit of immersion, the light Fenton list include elevator pump,
H2O2/H2SO4Head tank, series connection stainless steel column, the positive permeation unit of the immersion include positive permeation unit intake pool, draw
Flow container and draw pump, H2O2/H2SO4Head tank and elevator pump are separately connected series connection stainless steel column import by the road, in each series connection
It is provided with quartz ampoule in stainless steel column, ultraviolet light or visible light emitting diode are provided in the quartz ampoule, in every stone
Bead of the outside of English pipe filled with load light fenton catalyst, is provided with sheet frame in the positive permeation unit intake pool
Formula forward osmosis membrane component is connected in plate and frame forward osmosis membrane component lower end and draws liquid input pipe, draws the liquid input pipe other end
It is drawn pump and is connected to and draw flow container, drawn to be connected with above flow container and draw liquid efferent duct, draw the connection of the liquid efferent duct other end
To the upper end of plate and frame forward osmosis membrane component.
Moreover, the entrance end in each series connection stainless steel column is equipped with strainer, the opening of sieve of the series connection stainless steel column
Diameter is less than bead outer diameter.
Moreover, the plate and frame forward osmosis membrane component is immersed in positive permeation unit intake pool, the forward osmosis membrane group
The forward osmosis membrane piece active layer of part is contacted with the water outlet of light Fenton unit, and forward osmosis membrane piece mechanical support layer is contacted with liquid is drawn.
Moreover, the H2O2/H2SO4Head tank and series connection stainless steel column material are titanium steel.
A kind of smooth Fenton-is just permeating the integrated apparatus application method of Combined Treatment bio-refractory organic wastewater, the party
Method includes light Fenton process and positive process of osmosis, the specific steps are as follows:
(1) light Fenton process carries out in light Fenton unit, and waste water containing recalcitrant pollutant flows through light Fenton unit,
Ultraviolet light or visible light emitting diode provide ultraviolet or visible light, load the bead of light fenton catalyst through ultraviolet light or can
After light-exposed irradiation, with H2O2Generate hydroxyl free radical OH isoreactivity substance, transitory efficient degradation or the useless organism in water difficulty drop of conversion
Solve organic pollutant；
(2) positive process of osmosis carries out in the positive permeation unit of immersion, and the waste water after light Fenton unit flows into positive infiltration
Unit intake pool, plate and frame forward osmosis membrane component is immersed in positive permeation unit intake pool, inside plate and frame module under
Supreme flowing high concentration draws liquid, is higher than waste water infiltration pressure because drawing liquid osmotic pressure, forms permeable pressure head in forward osmosis membrane two sides,
Under permeable pressure head driving, water purification is spread through forward osmosis membrane to liquid side is drawn in positive permeation unit intake pool, and light Fenton mistake
Incomplete organic pollutant is degraded or converted to journey by effectively catching outside film in positive permeation unit intake pool；
(3) treated above-mentioned steps (1) and (2), and waste water can be further and at bioanalysis or other physics, chemical method water
Science and engineering skill is used in conjunction, and improves wastewater treatment rate and reclamation rate.
Moreover, step (1) treated waste water can be back to light Fenton unit after the water outlet of light Fenton unit according to water quality
Advanced treating again.
Moreover, light Fenton process is run under the conditions of pH≤7.
Moreover, the bead of the load light fenton catalyst includes ultraviolet light light fenton catalyst bead and visible
Light light fenton catalyst bead.
Moreover, the ultraviolet light light fenton catalyst bead is the preparation method is as follows: by 0-10mmol cobalt nitrate, sulfuric acid
Ferrous iron, ammonium fluoride, urea are dissolved in be thoroughly mixed in deionized water after, above-mentioned mixed solution is transferred in polytetrafluoroethylene (PTFE)
In > 100 DEG C water thermal responses in the reaction kettle of lining, product second alcohol and water, be made after rinse is dry repeatedly the cobalt of 3D structure/
Iron layered double hydroxide (3D-LDHs), above-mentioned 3D-LDHs are distributed in 0g-10g/L iron chloride, and bead immerses 0g-
In 10g/L tannic acid solution after 20-60 minutes, the bead that surface is coated with tannic acid is again dipped into and is dispersed with 3D-LDHs's
In iron chloride, the bead of load light fenton catalyst is made after rinse is dry repeatedly through ultrapure water.
Moreover, the visible light light fenton catalyst bead is the preparation method is as follows: take melamine Celsius with 2.3
After degree/min heating rate is heated to 550 degrees Celsius, then with 5 degrees celsius/minute heating rates 500 degrees Celsius are heated to, is made
Graphite phase carbon nitride (g-C3N4), by 0-10mmol cobalt nitrate, ferrous sulfate, ammonium fluoride, urea are dissolved in deionized water sufficiently
After being stirred, g-C3N4 is added, above-mentioned mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining Celsius > 100
Spend hydro-thermal reaction after a certain period of time, product is loaded with the graphite phase carbon nitride that 3D structure is made after second alcohol and water repeatedly rinse drying
Cobalt/iron layered double hydroxide (g-C3N4/3D-LDHs), above-mentioned g-C3N4/3D-LDHs are distributed to 0g-10g/L chlorination
In iron, in bead immersion 0g-10g/L tannic acid solution after 20-60min, the bead that surface is coated with tannic acid is soaked again
Enter to be dispersed in the iron chloride of g-C3N4/3D-LDHs after a certain period of time, visible light light is made after rinse is dry repeatedly through ultrapure water
Fenton catalyst bead.
The advantages and positive effects of the present invention are:
1, present apparatus light Fenton processing unit can reduce recalcitrant pollutant concentration, alleviate the outer concentration difference of positive process of osmosis
Polarization phenomena, and then forward osmosis membrane organic pollution load and organic contamination risk are reduced, while solving conventional film process operation
The high COD concentrated water of water inlet end handles handling problems afterwards；Ultraviolet light can effectively remove microorganism in waste water in light Fenton processing unit, save
Complicated Wastewater Pretreatment bactericidal device and process are gone, forward osmosis membrane microbial contamination risk is eliminated.
2, present apparatus light Fenton unit uses filled type configuration, and the bead of light fenton catalyst load is filled in light source four
In week, the efficiency of light energy utilization is high, compares micro-nano graininess light fenton catalyst and is easier to recycle and recycle, and light fenton catalyst is negative
It is fragrant to the pollution risk of downstream forward osmosis membrane and immobilized formula light that the bead of load reduces the heterogeneous smooth fenton catalyst of micro-nano
The plating film catalyst that pauses is compared, and filled type close structure is porous, and half fill pattern of light fenton catalyst does not influence water and pollutant passes
Matter, anti-current-rush ability are strong.
3, the present apparatus uses ultraviolet light-emitting diodes for light Fenton light source, overcomes that traditional UV lamps calorific value is big, energy
The low problem of metric density is not required to install additional cooling system.
4, the present apparatus utilizes positive infiltration while effectively degrading using light Fenton processing unit or converting organic pollutant
The retention light Fenton process degradation of film selective penetrated property converts incomplete organic pollutant, and the positive permeation unit of immersion is using leaching
Do not have the positive infiltration structure of formula, without water inlet end circulating pump and water inlet tank body, compact overall structure, low energy consumption, easily with other techniques or
Device joint, the active material that light Fenton unit generates are converted in contaminant degradation and are consumed into positive permeation unit transition process
To the greatest extent, strong oxidizing property will not influence the stability of film, and wastewater treatment rate is high, effect is good, be suitable for promoting the use of.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention, in which:
1- elevator pump, 2-H2O2/H2SO4Head tank, 3- series connection stainless steel column, 4- quartz ampoule, 5- ultraviolet light or visible light hair
Optical diode, the bead of 6- load light fenton catalyst, 7- strainer, 8- plate and frame forward osmosis membrane component, 9- draw liquid input
Pipe, 10- draw pump, and 11- draws flow container, and 12- draws liquid efferent duct, the positive permeation unit intake pool of 13-.
Specific embodiment
The invention will be further described with reference to the accompanying drawing and by specific embodiment, and following embodiment is descriptive
, it is not restrictive, this does not limit the scope of protection of the present invention.
A kind of smooth Fenton-is just permeating the integrated apparatus of Combined Treatment bio-refractory organic wastewater, as shown in Figure 1, packet
Light Fenton unit and the positive permeation unit of immersion are included, light Fenton unit connects the positive permeation unit of immersion, the light Fenton list
Including elevator pump 1, H2O2/H2SO4Head tank 2, series connection stainless steel column 3, the positive permeation unit of the immersion include that positive infiltration is single
First intake pool 13 draws flow container 11 and draws pump 10, H2O2/H2SO4It is stainless that head tank and elevator pump are separately connected series connection by the road
Steel column import is provided with quartz ampoule 4 in each series connection stainless steel column, ultraviolet light or visible light is provided in the quartz ampoule
Light emitting diode 5, quartz ampoule selects quartz material to ensure the effective transmission of ultraviolet light/visible light, in the outside of every quartz ampoule
Bead 6 filled with load light fenton catalyst is equipped with strainer 7, strainer in the entrance end of each series connection stainless steel column
The bead of load light fenton catalyst can be effectively prevented to be lost from stainless steel column due to waste water flowing is washed away.
Blend H2O2/H2SO4Waste water successively from series connection stainless steel column on the left of import flow into, be filled through formula by gravity
The bead for loading light fenton catalyst reaches stainless steel column bottom, then successively to concatenated stainless steel column right side flow, light is fragrant
Gap guarantees waste water and loads the bead of light fenton catalyst to come into full contact with and do not influence waste water and pollution between catalyst
Object mass transfer.
It is provided with plate and frame forward osmosis membrane component 8 in the positive permeation unit intake pool, the plate and frame forward osmosis membrane
Component is immersed in positive permeation unit intake pool, is connected in plate and frame forward osmosis membrane component lower end and is drawn liquid input pipe 9, draws
The liquid input pipe other end, which is drawn pump and is connected to, draws flow container.It draws to be connected with above flow container and draws liquid efferent duct 12, draw liquid
The efferent duct other end is connected to the upper end of plate and frame forward osmosis membrane component.
The water outlet of light Fenton unit flows into positive permeation unit intake pool, until submergence plate and frame forward osmosis membrane component.Draw liquid
Stored in drawing flow container, draw liquid and drawn pump conveying, drawn liquid input pipe below plate and frame forward osmosis membrane component into
Enter, is circulated from bottom to top in plate and frame forward osmosis membrane component.Because drawing liquid osmotic pressure higher than waste water infiltration pressure, just seeping
Permeable membrane two sides formed permeable pressure head, under the driving of permeable pressure head, in positive permeation unit intake pool water purification through forward osmosis membrane to
Draw liquid side diffusion, and light Fenton process degradation or convert incomplete organic pollutant by effectively catching outside forward osmosis membrane just
In permeation unit intake pool.Liquid is drawn in plate and frame forward osmosis membrane component to dilute because of the entrance of water purification, it is diluted to draw liquid Jie
Drawing to enter after the outflow of liquid efferent duct and draw in flow container and recycle by plate and frame forward osmosis membrane component upper end.
A kind of smooth Fenton-is just permeating the integrated apparatus application method of Combined Treatment bio-refractory organic wastewater, the party
Method includes light Fenton process and positive process of osmosis, the specific steps are as follows:
(1) light Fenton process carries out in light Fenton unit, and waste water containing recalcitrant pollutant flows through light Fenton unit,
Ultraviolet light or visible light emitting diode provide ultraviolet or visible light, load the bead of light fenton catalyst through ultraviolet light or can
After light-exposed irradiation, with H2O2Generate hydroxyl free radical OH isoreactivity substance, transitory efficient degradation or the useless organism in water difficulty drop of conversion
Organic pollutant is solved, light Fenton process runs under the conditions of pH≤7, and treated that waste water is discharged from light Fenton unit for step (1)
After light Fenton unit advanced treating again can be back to according to water quality.
(2) positive process of osmosis carries out in the positive permeation unit of immersion, and the waste water after light Fenton unit flows into positive infiltration
Unit intake pool, plate and frame forward osmosis membrane component is immersed in positive permeation unit intake pool, inside plate and frame module under
Supreme flowing high concentration draws liquid, is higher than waste water infiltration pressure because drawing liquid osmotic pressure, forms permeable pressure head in forward osmosis membrane two sides,
Under permeable pressure head driving, water purification is spread through forward osmosis membrane to liquid side is drawn in positive permeation unit intake pool, and light Fenton mistake
Incomplete organic pollutant is degraded or converted to journey by effectively catching outside film in positive permeation unit intake pool.
(3) treated above-mentioned steps (1) and (2), and waste water can be further and at bioanalysis or other physics, chemical method water
Science and engineering skill is used in conjunction, and improves wastewater treatment rate and reclamation rate.
The bead for loading light fenton catalyst includes that ultraviolet light light fenton catalyst bead and visible light light Fenton are urged
Agent bead.Ultraviolet light light fenton catalyst bead is the preparation method is as follows: by 0-10mmol cobalt nitrate, ferrous sulfate, fluorine
Change ammonium, urea are dissolved in after being thoroughly mixed in deionized water, and above-mentioned mixed solution is transferred to the anti-of polytetrafluoroethyllining lining
It answers in > 100 DEG C water thermal responses in kettle, cobalt/iron layer shape of 3D structure is made in product second alcohol and water after rinse is dry repeatedly
Double-metal hydroxide (3D-LDHs), above-mentioned 3D-LDHs are distributed in 0g-10g/L iron chloride, and bead immerses 0g-10g/L
In tannic acid solution after 20-60 minutes, the bead that surface is coated with tannic acid is again dipped into the iron chloride for being dispersed with 3D-LDHs
In, the bead of load light fenton catalyst is made after rinse is dry repeatedly through ultrapure water.Visible light light fenton catalyst glass
After pearl is the preparation method is as follows: take melamine to be heated to 550 degrees Celsius with 2.3 degrees celsius/minute heating rates, then it is Celsius with 5
Degree/min heating rate is heated to 500 degrees Celsius, is made graphite phase carbon nitride (g-C3N4), by 0-10mmol cobalt nitrate, sulfuric acid
Ferrous iron, ammonium fluoride, urea are dissolved in be thoroughly mixed in deionized water after, be added g-C3N4, above-mentioned mixed solution is transferred to
In the reaction kettle of polytetrafluoroethyllining lining > 100 DEG C water thermal responses after a certain period of time, product second alcohol and water rinse repeatedly
Graphite phase carbon nitride Supported Co/iron layered double hydroxide (g-C3N4/3D-LDHs) of 3D structure is made after drying, on
It states g-C3N4/3D-LDHs to be distributed in 0g-10g/L iron chloride, bead immerses 20-60min in 0g-10g/L tannic acid solution
Afterwards, the bead that surface is coated with tannic acid is again dipped into the iron chloride for be dispersed with g-C3N4/3D-LDHs after a certain period of time,
Visible light light fenton catalyst bead is made after rinse is dry repeatedly through ultrapure water.
The H of the present apparatus2O2/H2SO4Head tank material is titanium steel, and series connection stainless steel column is cylinder, and material is similarly titanium
Steel.Light Fenton light source is ultraviolet light or visible light emitting diode, is not required to install additional cooling system.Light in light Fenton unit
Fenton light source can open also intermittent open simultaneously.Light Fenton unit uses filled type configuration, the load of light fenton catalyst
Bead is filled in light source surrounding, and packed height is slightly above light source.Load light Fenton catalysis in the bead of light fenton catalyst
Agent is chemical method synthesis with ultraviolet or visible light Fenton catalytic effect ferrum-based catalyst film layer.Load the catalysis of light Fenton
It is modified again after the bead of agent is recyclable to guarantee its light Fenton catalytic activity and reclamation rate.
The aperture of filter screen for stainless steel column of connecting is less than bead outer diameter, prevents load light Fenton catalysis in series connection stainless steel column
The bead of agent is lost due to waste water flowing is washed away.It draws liquid and uses the high concentration salt solutions for being higher than waste water infiltration pressure.Every group of plate
Frame forward osmosis membrane component is made of two panels forward osmosis membrane piece, and the forward osmosis membrane piece active layer is discharged with light Fenton unit outwardly
Contact, forward osmosis membrane piece mechanical support layer inwardly with draw liquid and contact.Drawing liquid can be sharp again by drawing the recycling of liquid recyclable device
With.
Plate and frame forward osmosis membrane component is immersed in positive permeation unit intake pool, the positive infiltration of the forward osmosis membrane component
Diaphragm active layer is contacted with the water outlet of light Fenton unit, and forward osmosis membrane piece mechanical support layer is contacted with liquid is drawn.Plate and frame just permeates
U.S. HTI company CTA-ES, CTA-W, CTA-NW Triafol T forward osmosis membrane, TFC-ES polyamides can be selected in membrane module diaphragm
Amine utilized thin film composite membranes, Sterlitech company, U.S. Aquaporin-TFC aquaporin-polyam ide TLC composite membrane；
By test of many times, water treatment efficiency is good, and specific test data is as follows:
PH is adjusted to acid condition, and ultraviolet light/visible light emitting diode opens 30min-180min light Fenton unit pair
Bio-refractory organic wastewater COD removal rate is up to 80% or more, TOC removal rate up to 60% or more；When plate and frame forward osmosis membrane group
It is more than 80% to COD removal rate when part diaphragm active layer is discharged towards light Fenton unit.
The present invention can also handle salinity containing dissolubility, heavy metal ion and micro- in addition to handling bio-refractory organic wastewater
The waste water of biology, can also be with other physics, chemistry, bioanalysis water treatment technology and the above-mentioned waste water of device Combined Treatment.By upper
Description is stated, those skilled in the art can carry out multiplicity without departing from the scope of the technological thought of the present invention' completely
Change and modification are all within protection scope of the present invention.Unaccomplished matter of the invention belongs to the public affairs of those skilled in the art
Know common sense.
Claims (10)
1. a kind of integrated apparatus of smooth Fenton-just infiltration Combined Treatment bio-refractory organic wastewater, it is characterised in that: including
Light Fenton unit and the positive permeation unit of immersion, light Fenton unit connect the positive permeation unit of immersion, the light Fenton list packet
Include elevator pump, H2O2/H2SO4Head tank, series connection stainless steel column, the positive permeation unit of the immersion include positive permeation unit into
Pond draws flow container and draws pump, H2O2/H2SO4Head tank and elevator pump are separately connected series connection stainless steel column import by the road,
It is provided with quartz ampoule in each series connection stainless steel column, ultraviolet light or visible light light-emitting diodes are provided in the quartz ampoule
Pipe, in bead of the outside of every quartz ampoule filled with load light fenton catalyst, in the positive permeation unit intake pool
In be provided with plate and frame forward osmosis membrane component, be connected in plate and frame forward osmosis membrane component lower end and draw liquid input pipe, draw liquid
The input pipe other end, which is drawn pump and is connected to, draws flow container, draws to be connected with above flow container and draws liquid efferent duct, draws liquid output
The pipe other end is connected to the upper end of plate and frame forward osmosis membrane component.
2. a kind of integration of smooth Fenton-according to claim 1 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: be equipped with strainer, the strainer of the series connection stainless steel column in the entrance end of each series connection stainless steel column
Aperture is less than bead outer diameter.
3. a kind of integration of smooth Fenton-according to claim 1 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: the plate and frame forward osmosis membrane component is immersed in positive permeation unit intake pool, the forward osmosis membrane
The forward osmosis membrane piece active layer of component is contacted with the water outlet of light Fenton unit, and forward osmosis membrane piece mechanical support layer is contacted with liquid is drawn.
4. a kind of integration of smooth Fenton-according to claim 1 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: the H2O2/H2SO4Head tank and series connection stainless steel column material are titanium steel.
5. a kind of integrated apparatus application method of smooth Fenton-just infiltration Combined Treatment bio-refractory organic wastewater, feature
Be: method includes light Fenton process and positive process of osmosis, the specific steps are as follows:
(1) light Fenton process carries out in light Fenton unit, and waste water containing recalcitrant pollutant flows through light Fenton unit, ultraviolet
Light or visible light emitting diode provide ultraviolet or visible light, load the bead of light fenton catalyst through ultraviolet light or visible light
After irradiation, with H2O2Hydroxyl free radical OH isoreactivity substance is generated, there is bio-refractory in transitory efficient degradation or conversion waste water
Machine pollutant；
(2) positive process of osmosis carries out in the positive permeation unit of immersion, and the waste water after light Fenton unit flows into positive permeation unit
Intake pool, plate and frame forward osmosis membrane component are immersed in positive permeation unit intake pool, inside plate and frame module from the bottom to top
Flowing high concentration draws liquid, because drawing liquid osmotic pressure higher than waste water infiltration pressure, forms permeable pressure head in forward osmosis membrane two sides, is seeping
Under saturating pressure differential, water purification is spread through forward osmosis membrane to liquid side is drawn in positive permeation unit intake pool, and light Fenton process drops
Incomplete organic pollutant is solved or converted by effectively catching outside film in positive permeation unit intake pool；
(3) treated above-mentioned steps (1) and (2) waste water can further with bioanalysis or other physics, chemical method water process work
Skill is used in conjunction, and improves wastewater treatment rate and reclamation rate.
6. a kind of integration of smooth Fenton-according to claim 5 just infiltration Combined Treatment bio-refractory organic wastewater
Device application method, it is characterised in that: step (1) treated waste water can be back to after the water outlet of light Fenton unit according to water quality
Light Fenton unit advanced treating again.
7. a kind of integration of smooth Fenton-according to claim 5 just infiltration Combined Treatment bio-refractory organic wastewater
Device application method, it is characterised in that: light Fenton process is run under the conditions of pH≤7.
8. a kind of integration of smooth Fenton-according to claim 1 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: the bead of the load light fenton catalyst include ultraviolet light light fenton catalyst bead and
Visible light light fenton catalyst bead.
9. a kind of integration of smooth Fenton-according to claim 8 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: the ultraviolet light light fenton catalyst bead the preparation method is as follows: by 0-10mmol cobalt nitrate,
Ferrous sulfate, ammonium fluoride, urea are dissolved in be thoroughly mixed in deionized water after, above-mentioned mixed solution is transferred to polytetrafluoroethyl-ne
In > 100 DEG C water thermal responses in the reaction kettle of alkene liner, 3D structure is made after rinse is dry repeatedly in product second alcohol and water
Cobalt/iron layered double hydroxide (3D-LDHs), above-mentioned 3D-LDHs is distributed in 0g-10g/L iron chloride, bead leaching
Enter in 0g-10g/L tannic acid solution after 20-60 minutes, the bead that surface is coated with tannic acid is again dipped into and is dispersed with 3D-
In the iron chloride of LDHs, the bead of load light fenton catalyst is made after rinse is dry repeatedly through ultrapure water.
10. a kind of integration of smooth Fenton-according to claim 8 just infiltration Combined Treatment bio-refractory organic wastewater
Device, it is characterised in that: the visible light light fenton catalyst bead is the preparation method is as follows: take melamine to take the photograph with 2.3
After family name degree/min heating rate is heated to 550 degrees Celsius, then with 5 degrees celsius/minute heating rates it is heated to 500 degrees Celsius, system
It obtains graphite phase carbon nitride (g-C3N4), by 0-10mmol cobalt nitrate, ferrous sulfate, ammonium fluoride, urea are dissolved in deionized water and filling
Divide after being stirred, g-C3N4 is added, above-mentioned mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining and is taken the photograph > 100
After a certain period of time, product is negative with the graphite phase carbon nitride that 3D structure is made after second alcohol and water repeatedly rinse drying for family name's degree hydro-thermal reaction
Cobalt/iron layered double hydroxide (g-C3N4/3D-LDHs) is carried, above-mentioned g-C3N4/3D-LDHs is distributed to 0g-10g/L chlorine
Change in iron, in bead immersion 0g-10g/L tannic acid solution after 20-60min, surface is coated with the bead of tannic acid again
Immersion is dispersed in the iron chloride of g-C3N4/3D-LDHs after a certain period of time, and visible light is made after rinse is dry repeatedly through ultrapure water
Light fenton catalyst bead.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485426.3A CN110204031B (en) | 2019-06-05 | 2019-06-05 | Integrated device for treating biologically-nondegradable organic wastewater by virtue of photo-Fenton-forward osmosis combination and application method of integrated device |
| AU2020100939A AU2020100939A4 (en) | 2019-06-05 | 2020-06-04 | Integrated apparatus for combined photo-fenton and forward osmosis treatment of non-biodegradable organic wastewater and use method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485426.3A CN110204031B (en) | 2019-06-05 | 2019-06-05 | Integrated device for treating biologically-nondegradable organic wastewater by virtue of photo-Fenton-forward osmosis combination and application method of integrated device |
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| CN110204031B CN110204031B (en) | 2021-11-02 |
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Cited By (5)
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| CN110813087A (en) * | 2019-12-03 | 2020-02-21 | 广东益诺欧环保股份有限公司 | Method and system for treating high-concentration VOCs waste gas |
| CN111718062A (en) * | 2020-06-16 | 2020-09-29 | 浙江工业大学义乌科学技术研究院有限公司 | Coupling process of efficient out-phase photoFenton and membrane bioreactor |
| CN112142167A (en) * | 2020-09-07 | 2020-12-29 | 南京智汇环境气象产业研究院有限公司 | Preparation method of layered double-metal hydroxide Co-Fe-LDH electro-catalytic Fenton reaction cathode plate |
| CN113697899A (en) * | 2021-09-07 | 2021-11-26 | 荆州市昌盛环保工程有限公司 | A high-efficient type fenton reaction unit for oily waste water |
| WO2022168519A1 (en) * | 2021-02-04 | 2022-08-11 | 国立研究開発法人農業・食品産業技術総合研究機構 | Photocatalyst composition, method for producing same, and deodorizing agent |
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| CN115888774B (en) * | 2022-12-21 | 2024-07-05 | 东南大学 | Magnetic multi-element heterojunction photo-Fenton catalyst, preparation method, regeneration treatment system and treatment method |
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| AU2020100939A4 (en) | 2020-07-16 |
| CN110204031B (en) | 2021-11-02 |
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