CN110102187A - The method and device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane - Google Patents
The method and device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane Download PDFInfo
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- CN110102187A CN110102187A CN201910345951.5A CN201910345951A CN110102187A CN 110102187 A CN110102187 A CN 110102187A CN 201910345951 A CN201910345951 A CN 201910345951A CN 110102187 A CN110102187 A CN 110102187A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/10—Accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/022—Membrane sterilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/14—Use of concentrate
Abstract
The invention discloses a kind of methods of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane comprising following steps: a, the concentrated water for generating reverse osmosis/nanofiltration system are collected in concentrated water tank, are produced water and are collected in producing water pot；B, the pressure of freq uency conversion supercharging pump is reduced, the inlet valve of reverse osmosis/nanofiltration system is closed and produces water outlet valve；C, the concentrated water in the step a concentrated water tank is sent into air and liquid mixer, ozone is added in Xiang Suoshu air and liquid mixer；D, it will be pumped into the reverse osmosis/nanofiltration membrane component through catalytic ozonation treated concentrated water by the freq uency conversion supercharging in air and liquid mixer in the step c, production water in the production water pot enters in the reverse osmosis/nanofiltration membrane component, realizes the on-line cleaning to reverse osmosis/nanofiltration membrane.The problems such as fouling membrane can be effectively relieved in method of the invention, extend the service life of membrane module, solve conventional film cleaning way energy consumption height, secondary pollution, multiple disassembly and stoppage in transit is easily caused to cause mechanical wear.
Description
Technical field
The invention belongs to technical field of membrane, and in particular to and a kind of concentrated water catalytic ozonation on-line cleaning is reverse osmosis/nanofiltration
The method of film especially further relates to a kind of device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane.
Background technique
Membrane separation technique is excellent with its effluent quality, occupied area is small, effluent quality fluctuation is small and is easily achieved automatic control
The advantages that processed, becomes the hot spot of research and the application of current water treatment field.With the increasingly mature and cost of membrane separation technique
Decline, membrane separation technique is applied to the processing of water and waste water more and more widely, cost, mode accordingly, with respect to Membrane cleaning
And whether generates secondary pollution problems and all the more attract attention.
Currently, the cleaning way of film is broadly divided into physical cleaning and chemical cleaning.Physical cleaning mainly includes rinsing, recoiling
It washes and ultrasonic cleaning.It rinses and backwash is to rinse film surface or reversed punching using high-velocity flow, air-flow or mixing wastewater with air stream
Fenestra road is washed, application is more universal, but backwash is generally not used for rolling nanofiltration membrane and coiled reverse osmosis membrane component.Ultrasonic cleaning
It is the pollutant of the high-energy destruction film surface generated using ultrasonic pulse, cleaning effect is good, but may destroy the knot of film
Structure, higher cost.Chemical cleaning is chemically reacted using the pollutant of the chemical agents such as acid, alkali and film surface, cleaning effect
Fruit is good, high-efficient, but is easy to produce secondary pollution or leads to the irreversible damage of film, higher cost.
The pollution of reverse osmosis membrane or nanofiltration membrane is generally divided into reversible membrane fouling and irreversible membrane fouling.The reversible membrane fouling layer structure of matter
It is loose, it is not close with film surface absorption, it can be removed under hydrodynamic cleaning.Irreversible membrane fouling layer is generally contacted with film surface closely, water
Power flushing cannot remove, and only reacted and removed by chemical agent.Common reverse osmosis membrane or nanofiltration membrane chemical cleaning method are
Reverse osmosis or nanofiltration device is connect with cleaning pump and cleaning solution hold-up tank, prepares cleaning solution in cleaning solution hold-up tank, according to
The type adjustment temperature and pH value of film.Then cleaning solution is pumped into reverse osmosis or nanofiltration system by starting cleaning pump, will be in system
Retain water and after initial dirtier cleaning excludes liquid discharge, wash cycles 1 hour or longer time.It can be used and follow as needed
Ring cleans and soaking cycle, and after chemical cleaning, low-pressure washing can be carried out with reverse osmosis or nanofiltration product water, is removed reverse osmosis
Or the residual fraction of the chemical agent in nanofiltration system.In addition, for two sections or more of reverse osmosis or nanofiltration system, it is general to be segmented
Cleaning, to guarantee that circular flow will not be too low to first segment and final stage will not be too high, and prevents from being washed off in first segment
Pollutant be deposited in the film surface of second segment again.Terminate to put into operation again in the cleaning of reverse osmosis or nanofiltration system
When, initial product water should discharge, and when conductance, pH value, which reach technique, to be required, reverse osmosis or nanofiltration system can put into operation.Due to
Chemical cleaning especially high ph-values cleaning changes the charge property of reverse osmosis membrane or nanofiltration surface, and the product water water quality at initial stage is not
Stablize, to obtain stable product water water quality, it may be necessary to a few houres to several days recovery times.
Therefore, it is badly in need of developing a kind of method that can fast implement Membrane cleaning, can be improved cleaning efficiency, enhancing cleaning effect
Fruit extends the service life of membrane module.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membranes
Method, fouling membrane can be effectively relieved in this method, extend the service life of membrane module, solve conventional film cleaning way energy consumption
It is high, easily cause secondary pollution, the problems such as repeatedly disassembly and stoppage in transit cause mechanical wear.
In order to solve the above technical problems, the present invention provides a kind of concentrated water catalytic ozonation on-line cleaning it is reverse osmosis/receive
The method of filter membrane, includes the following steps:
A, the concentrated water for generating reverse osmosis/nanofiltration system is collected in concentrated water tank, is produced water and is collected in producing water pot；
B, the pressure of freq uency conversion supercharging pump is reduced, the inlet valve of reverse osmosis/nanofiltration system is closed and produces water outlet valve, makes reverse osmosis
The process of osmosis opposite with when production water running process occurs in thoroughly/nanofiltration membrane component；
C, the concentrated water in the step a concentrated water tank is sent into air and liquid mixer, is added in Xiang Suoshu air and liquid mixer smelly
Oxygen, concentrated water and ozone are sufficiently mixed in the air and liquid mixer；
D, it will obtain that treated that concentrated water passes through the frequency conversion through catalytic ozonation in the step c in air and liquid mixer
Pressurization is pumped into the reverse osmosis/nanofiltration membrane component, and the production water produced in water pot enters the reverse osmosis/nanofiltration membrane component
It is interior, the process of osmosis contrary with when production water running occurs, realizes the on-line cleaning to reverse osmosis/nanofiltration membrane.
The method of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the step c is by institute
The concentrated water stated in step a concentrated water tank is sent into bipolar membrane module, and the acid solution of generation enters in acid storage tank, and the lye of generation enters storage
It, will be in the acid storage tank when major pollutants are inorganic pollution in the water inlet of reverse osmosis/nanofiltration membrane system processing in alkali tank
Acid solution mixed with the salting liquid obtained after the bipolar film process, be mixed into Bipolar Membrane treated concentrated water, be sent into gas
In liquid mixer, it is added ozone in Xiang Suoshu air and liquid mixer, Bipolar Membrane treated concentrated water and ozone are in the gas-liquid mixed
It is sufficiently mixed in device.
The method of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the step c is by institute
The concentrated water stated in step a concentrated water tank is sent into bipolar membrane module, and the acid solution of generation enters in acid storage tank, and the lye of generation enters storage
It, will be in the storage alkali tank when major pollutants are organic pollutant in the water inlet of reverse osmosis/nanofiltration membrane system processing in alkali tank
Lye mixed with the salting liquid obtained after the bipolar film process, be mixed into Bipolar Membrane treated concentrated water, be sent into gas
In liquid mixer, it is added ozone in Xiang Suoshu air and liquid mixer, Bipolar Membrane treated concentrated water and ozone are in the gas-liquid mixed
It is sufficiently mixed in device.
The method of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the reverse osmosis/nanofiltration
After system produces water running 10-30 minutes, closes inlet valve and produce water outlet valve, reduce the pressure of freq uency conversion supercharging pump, carry out online
Infiltration cleaning reverse osmosis/nanofiltration membrane 30-300 seconds.
The present invention also provides a kind of device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, the devices
Including freq uency conversion supercharging pump, reverse osmosis/nanofiltration membrane component, produce water pot, concentrated water tank, air and liquid mixer and ozone generator, the change
The outlet of frequency booster pump is connect with the water inlet of the membrane module, and the production mouth of a river of the membrane module is connect with the production water pot, institute
The concentrated water outlet for stating membrane module connect with the concentrated water tank water inlet, the concentrated water tank concentrated water export and the air and liquid mixer into
The connection of liquid mouth, the air and liquid mixer air inlet are connect with the ozone generator, the air and liquid mixer outlet and the change
The connection of frequency booster pump.
The device of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein described device further includes double
Pole membrane module, the bipolar membrane module setting are described between concentrated water tank concentrated water outlet and the air and liquid mixer inlet
The salting liquid outlet of bipolar membrane module is connect with the air and liquid mixer inlet, and the acid solution outlet of the bipolar membrane module passes through
Acid solution outlet valve is connect with the air and liquid mixer inlet, the lye export of the bipolar membrane module by lye export valve with
The air and liquid mixer inlet connection.
The device of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the device further includes storage acid
Tank and and storage alkali tank, the acid solution outlet connection of the acid storage tank and the bipolar membrane module, the storage alkali tank and the Bipolar Membrane
The lye export of component connects.
The device of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the reverse osmosis/nanofiltration
Membrane module is rolled film or plate membrane.
The device of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein be arranged on the concentrated water tank
Throw salt mouth.
The device of above-mentioned concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, wherein the device further includes pre- place
Component is managed, the upstream of the freq uency conversion supercharging pump is arranged in the pre-processing assembly.
The method and apparatus of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane of the invention have following beneficial
Effect:
1, methods and apparatus of the present invention permeate cleaning when do not need to remove membrane module, also need not external equipment, but
Change the direction of membrane module position pure water infiltration by changing the size of high-pressure pump generation pressure, to reach online to film group
The purpose that part is cleaned reduces the damage to membrane module, extends the service life of membrane module, reduces technical process
Operating cost；
2, methods and apparatus of the present invention is not required in addition prepare cleaning solution pair using the concentrated water of generation as infiltration cleaning solution
Membrane module is cleaned, and is reduced the water resource waste that concentrated water discharge may cause, is realized NF concentrated water reuse；
3, methods and apparatus of the present invention is added ozone in air and liquid mixer and mixes with concentrated water, and ozone is to dirty in concentrated water
Dye object plays the role of processing, meanwhile, ozone plays bactericidal effect, alleviates the biological pollution of membrane module significantly；
4, in methods and apparatus of the present invention, additionally use what bipolar membrane module generated reverse osmosis/nanofiltration system itself
Concentrated water electricity is dissociated into acid solution and lye, and is carried out by force using these acid solutions and lye to the inorganic pollution of film surface and organic contamination
Change infiltration cleaning, the water flux after capable of being obviously improved Membrane cleaning realizes waste water money preferably using the concentrated water that itself is generated
Source reduces the pollution that concentrated water discharge may cause, while voltage needed for Bipolar Membrane is extremely low, can be with compared to offline cleaning
It is energy saving；A possibility that cleaning of itself concentrated water also reduces secondary pollution compared to offline chemical cleaning；
5, in method of the invention, infiltration cleaning process can not influence process operation by robot control system(RCS) automatic running
Routine use, and the cleaning of multifrequency time reduces each cleaning difficulty in the short time, increases the service life of membrane module；
6, in method of the invention, in reverse osmosis/nanofiltration system production water running, infiltration cleaning process, pump can high-low pressure
Alternate run, but not open and shut down repeatedly, reduce the mechanical loss that switch pump may cause；
7, in the device of the invention, concentrated water tank, which is equipped with, throws salt mouth, can be with when concentrated water concentration is not enough to carry out infiltration cleaning
The mode that inorganic salts are additionally added in concentrated water tank enhances infiltration cleaning effect.
Detailed description of the invention
Fig. 1 is the schematic device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane of the present invention；
Fig. 2 is infiltration Cleaning principle figure；
Fig. 3 is bipolar membrane electrodialysis water decomposition schematic diagram.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
One, the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane
Embodiment 1
As shown in Figure 1, the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane of the invention includes frequency conversion
Booster pump P, reverse osmosis/nanofiltration membrane component 2, water pot 3, concentrated water tank 4, air and liquid mixer 10 and ozone generator 9, freq uency conversion supercharging are produced
The outlet of pump P is connect with the water inlet of membrane module 2, and the production mouth of a river of membrane module 2 is connect with water pot 3 is produced, the concentrated water outlet of membrane module 2
It is connect with the water inlet of concentrated water tank 4, the concentrated water outlet of concentrated water tank 4 is connect with the inlet of air and liquid mixer 10, air and liquid mixer
10 air inlet is connect with ozone generator 9, and the outlet of air and liquid mixer 10 is connect with freq uency conversion supercharging pump P.Preferably, of the invention
Device also set up pre-processing assembly 1, pre-processing assembly 1 is connect by inlet valve F1 with freq uency conversion supercharging pump P.
Further, the device of the invention is additionally provided with bipolar membrane module 5 between concentrated water tank 4 and air and liquid mixer 10,
The acid solution outlet of bipolar membrane module 5 is connect with acid storage tank 6, and lye export is connect with storage alkali tank 7.Concentrated water passes through bipolar membrane module 5
The salting liquid outlet obtained after processing is connect with 10 inlet of air and liquid mixer, and acid storage tank 6 passes through acid solution outlet valve F6 and gas-liquid
The connection of 10 inlet of mixer, storage alkali tank 7 are connect by lye export valve F7 with 10 inlet of air and liquid mixer.
Further, salt mouth 11 is thrown in setting on concentrated water tank 4, can be with when concentrated water concentration is not enough to carry out infiltration cleaning
The mode that inorganic salts are additionally added in concentrated water tank enhances infiltration cleaning effect.The bottom of concentrated water tank also sets up sewage draining exit, pollution
Concentrated water tank is discharged via blowdown valve F3 by sewage draining exit in serious concentrated water, into subsequent sewage second-level treatment process.
The concentrated water of concentrated water tank 4 is exported is arranged switching valve F4 between bipolar membrane module 5, and switching valve F4 can be in a, b, c
It is switched at three ports, to realize that the production water running of reverse osmosis/nanofiltration system, concentrated water catalytic ozonation are permeated clearly online
It washes and concentrated water Bipolar Membrane combination catalytic ozonation permeates cleaning reverse osmosis/nanofiltration membrane online.Switching valve F4, which can be used, to be appointed
The valve for realizing the conversion of pipeline direction of what general type, such as three-way ball valve.
At least one reverse osmosis/nanofiltration membrane component, including rolled film, plate membrane etc. are equipped in membrane module 2.
Two, the method for concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane
2 concentrated water catalytic ozonation of embodiment permeates cleaning method online:
(1) reverse osmosis/nanofiltration system produces water running:
Freq uency conversion supercharging pumps P high-voltage operation, and valve F5, F10 are normally opened, opens inlet valve F1 and produces water outlet valve F2, switching valve
F4 meets port c, remaining valve is closed.
Water inlet is after pre-processing assembly 1, and by inlet valve F1, reverse osmosis is then entered under the action of freq uency conversion supercharging pumps P
Thoroughly/nanofiltration membrane component 2 carries out water process by membrane separating process, produces water and enters in production water pot 3, passes through and produce water outlet valve F2 weight
It newly comes into operation, concentrated water, which enters in concentrated water tank 4, to be stored.
(2) concentrated water catalytic ozonation permeates cleaning method online
Freq uency conversion supercharging pumps P low pressure operation, and valve F5, F10 are normally opened, closes inlet valve F1, produces water outlet valve F2, blowdown valve
F3, acid solution outlet valve F6, lye export valve F7, switching valve F4 meet port b, open valve F8 and F9.
After producing water running for a period of time, membrane module 2 pollutes, and so that freq uency conversion supercharging P is pumped low pressure operation at this time, simultaneously closes off
Inlet valve F1 and production water outlet valve F2, switching valve F4 transit ports b.Concentrated water in concentrated water tank 4 by switching valve F4, valve F5,
Valve F8 and spinner flowmeter I1 enter air and liquid mixer 10.Oxygen passes through valve F9, gas flowmeter I2 in oxygen tank 8, into
Enter ozone generator 9 and generate ozone/oxygen gas admixture of gas, is mixed into air and liquid mixer 10 with concentrated water.Contain the dense of ozone
Water enters membrane module 2 by valve F10 under the action of pumping P, and the permeable pressure head caused by concentrated water and the concentration difference of production water acts on
Under, it produces the production water in water pot 3 and the process of osmosis contrary with when production water running process occurs in membrane module 2, make to produce water transport
The cake layer and gel layer that film surface generates in membrane module 2 when row are loosened and are rinsed, while being made in fenestra road or film table
The salt dissolution of crystals that face is formed, infiltration Cleaning principle are shown in Fig. 2.It, can meanwhile when concentrated water concentration is not enough to carry out infiltration cleaning
The concentration of concentrated water is improved in a manner of through the additional inorganic salts of throwing salt mouth 11 on concentrated water tank 4, and then enhances infiltration cleaning effect.
It permeates after the completion of cleaning process, switching valve F4 is met into port c, while opening the inlet valve of reverse osmosis/nanofiltration system
F1 and production water outlet valve F2, is turned up the pressure of freq uency conversion supercharging pump P, and reverse osmosis/nanofiltration system produces water again, runs certain time
Afterwards, repeat cleaning-production water running-cleaning process.
Cleaning method is permeated in 3 concentrated water catalytic ozonation of embodiment combination Bipolar Membrane (pickling) online
(1) reverse osmosis/nanofiltration system produces water running:
Freq uency conversion supercharging pumps P high-voltage operation, and valve F5, F10 are normally opened, opens inlet valve F1 and produces water outlet valve F2, switching valve
F4 meets port c, remaining valve is closed.
Water inlet is after pre-processing assembly 1, and by inlet valve F1, reverse osmosis is then entered under the action of freq uency conversion supercharging pumps P
Thoroughly/nanofiltration membrane component 2 carries out water process by membrane separating process, produces water and enters in production water pot 3, passes through and produce water outlet valve F2 weight
It newly comes into operation, concentrated water, which enters in concentrated water tank 4, to be stored.
(2) cleaning method is permeated in concentrated water catalytic ozonation combination Bipolar Membrane (pickling) online
P low pressure operation is pumped, valve F5, F10 are normally opened, close inlet valve F1, production water outlet valve F2, blowdown valve F3, lye and go out
Mouth valve F7, switching valve F4 meet port a, open acid solution outlet valve F6, valve F8 and F9.
After producing water running for a period of time, membrane module 2 pollutes, if inorganic pollution concentration is higher in water inlet, passes through
The acid solution that bipolar membrane module 5 generates carries out infiltration cleaning/pickling superposition cleaning, bipolar membrane electrodialysis water decomposition principle to membrane module
See Fig. 3.Make to pump P low pressure operation at this time, simultaneously closes off inlet valve F1, produces water outlet valve F2, switching valve F4 transit ports a.Concentrated water
Concentrated water in tank 4 enters bipolar membrane module 5 by switching valve F4, and the acid solution of generation enters acid storage tank 6, and the lye of generation enters storage
Alkali tank 7, pipeline where remaining salting liquid enters valve F5 continue to participate in infiltration cleaning；Acid solution in acid storage tank 6 passes through acid solution
Outlet valve F6 is mixed before valve F8 with remaining salting liquid, enters air and liquid mixer 10 by valve F8 and spinner flowmeter I1；
Oxygen is by valve F9, gas flowmeter I2 in oxygen tank 8, into ozone generator 9 generate ozone/oxygen gas admixture of gas into
Enter air and liquid mixer 10 to mix with concentrated water.Acid concentrated water containing ozone enters membrane module by valve F10 under the action of pumping P
2, it in concentrated water and produces under the effect of permeable pressure head caused by the concentration difference of water, produces the production water in water pot 3 and occur in membrane module 2 and produce
Contrary process of osmosis when water running process, the cake layer and coagulate that film surface generates in membrane module 2 when making to produce water running
Glue-line is loosened and is rinsed, while making the salt dissolution of crystals that in fenestra road or film surface is formed, and the acidity of concentrated water is to this mistake
Journey has enhancing facilitation.Meanwhile when concentrated water concentration is not enough to carry out infiltration cleaning, the throwing on concentrated water tank 4 can be passed through
The mode of the additional inorganic salts of salt mouth 11 improves the concentration of concentrated water and the concentration of acid solution, and then enhances infiltration cleaning effect.
It permeates after the completion of cleaning process, switching valve F4 is met into port c, while opening the inlet valve of reverse osmosis/nanofiltration system
F1 and production water outlet valve F2, is turned up the pressure of freq uency conversion supercharging pump P, and reverse osmosis/nanofiltration system produces water again, runs certain time
Afterwards, repeat cleaning-production water running-cleaning process.
Cleaning method is permeated in 4 concentrated water catalytic ozonation of embodiment combination Bipolar Membrane (alkali cleaning) online
(1) reverse osmosis/nanofiltration system produces water running:
Freq uency conversion supercharging pumps P high-voltage operation, and valve F5, F10 are normally opened, opens inlet valve F1 and produces water outlet valve F2, switching valve
F4 meets port c, remaining valve is closed.
Water inlet is after pre-processing assembly 1, and by inlet valve F1, reverse osmosis is then entered under the action of freq uency conversion supercharging pumps P
Thoroughly/nanofiltration membrane component 2 carries out water process by membrane separating process, produces water and enters in production water pot 3, passes through and produce water outlet valve F2 weight
It newly comes into operation, concentrated water, which enters in concentrated water tank 4, to be stored.
(2) cleaning method is permeated in concentrated water catalytic ozonation combination Bipolar Membrane (alkali cleaning) online
P low pressure operation is pumped, valve F5, F10 are normally opened, close inlet valve F1, production water outlet valve F2, blowdown valve F3, acid solution and go out
Mouth valve F6, switching valve F4 meet port a, open lye export valve F7, valve F8 and F9.
After producing water running for a period of time, membrane module 2 pollutes, if higher into organic pollutants concentration, passes through
The lye that Bipolar Membrane generates carries out infiltration cleaning/alkali cleaning superposition cleaning to membrane module.Make to pump P low pressure operation at this time, simultaneously close off
Inlet valve F1, water outlet valve F2, switching valve F4 transit ports a are produced.Concentrated water in concentrated water tank 4 enters Bipolar Membrane by switching valve F4
Component 5, the acid solution of generation enter acid storage tank 6, and the lye of generation enters storage alkali tank 7, and remaining salting liquid enters where valve F5
Pipeline continues to participate in infiltration cleaning；The lye stored up in alkali tank 7 is mixed before valve F8 by lye export valve F7 and remaining salting liquid
It closes, enters air and liquid mixer 10 by valve F8 and spinner flowmeter I1；Oxygen passes through valve F9, gas flow in oxygen tank 8
I2 is counted, enters air and liquid mixer 10 into the generation ozone/oxygen gas admixture of gas of ozone generator 9 and is mixed with concentrated water.Containing smelly
The alkaline concentrated water of oxygen enters membrane module 2 by valve F10 under the action of pumping P, seeps caused by concentrated water and the concentration difference of production water
Under saturating differential pressure action, produces the production water in water pot 3 and occur to penetrate with contrary when producing water running process in membrane module 2
Journey, the cake layer and gel layer that film surface generates in membrane module 2 when making to produce water running are loosened and are rinsed, while making fenestra
In road or the organic pollutant dissolution of film surface formation, the alkalinity of concentrated water have enhancing facilitation to this process.Meanwhile when dense
When water concentration is not enough to carry out infiltration cleaning, it can be improved by way of the additional inorganic salts of throwing salt mouth 11 on concentrated water tank 4 dense
The concentration of water and the concentration of lye, and then enhance infiltration cleaning effect.
It permeates after the completion of cleaning process, switching valve F4 is met into port c, while opening the inlet valve of reverse osmosis/nanofiltration system
F1 and production water outlet valve F2, is turned up the pressure of freq uency conversion supercharging pump P, and reverse osmosis/nanofiltration system produces water again, runs certain time
Afterwards, repeat cleaning-production water running-cleaning process.
Embodiment 5 is reverse osmosis-and processing contains organic pollutant wastewater
The waste water of sodium alginate is mainly contained using the method processing of embodiment 2, condition is as follows: raw water SDI < 5, COD=
50mg/L, pH 6.5, free cl concn are lower than 0.1ppm, and inflow temperature is 25 DEG C；Membrane module 2 selects Hydranautics CPA3-LD anti-
Bitter coiled reverse osmosis membrane is polluted, initial water flux is 46.9L/ (hm2), operating pressure 1.6MPa, transmembrane pressure is low
In 0.1MPa；Oxygen flow is 0.25L/min, into the ozone/oxygen gas admixture of gas of air and liquid mixer 10, ozone concentration
For 12mg/L；After handling in air and liquid mixer 10 concentrated water, ozone concentration is lower than 5mg/L in gas-liquid mixture, can play
Certain bactericidal effect, and membrane material will not be made to deteriorate.Reverse osmosis produced water running 20min, water flux are reduced to initial flux
85.0% or so, start to carry out infiltration cleaning, scavenging period about 60s wherein about consumes in pipeline full of concentrated water and ozone mixture
When 5s or so, flux recovery is the 99.5% of initial flux；Repeat the process of reverse osmosis-infiltration cleaning after cleaning.
The waste water of sodium alginate is mainly contained using the method processing of the present embodiment, reverse osmosis-infiltration cleaning frequency is 20min-60s,
Repeating to be checked afterwards for 24 hours, water flux restores to the 95.3% of initial flux, at this point, effluent index is COD=8mg/L,
PH is 7.2, can carry out reuse.
Embodiment 6 is reverse osmosis-and processing contains organic pollutant wastewater
The waste water of sodium alginate is mainly contained using the method processing of embodiment 4, experiment condition is same as Example 5.?
Bipolar membrane module is increased under same experimental conditions, in the present embodiment, using lye to the organic contamination in reverse osmosis membrane assembly
Object carries out infiltration cleaning, and first sub-percolation cleaning can be such that the water flux of film restores to 99.8% or more；Repeat reverse osmosis-infiltration cleaning
Period, (20min-60s) was checked afterwards for 24 hours, and water flux can restore to the 98.2% of initial flux, at this point, effluent index is
COD=5mg/L, pH 7.3 can carry out reuse.
Comparative example 1
The cleaning method and experiment condition of comparative example 1 are same as Example 5, the difference is that in the method for comparative example 1
Do not use catalytic ozonation to handle concentrated water, concentrated water directly pass through pump P enter membrane module 2 and produce water permeate it is clear
It washes.
Wash result are as follows: reverse osmosis produced water running 20min, water flux are reduced to 85.0% of initial flux or so, start into
Row infiltration cleaning, scavenging period about 60s, wherein full of concentrated water about time-consuming 5s or so in pipeline, flux recovery is initial flux
94.3%；Repeat the process of reverse osmosis-infiltration cleaning after cleaning.It is mainly contained using the method processing of comparative example 1
The waste water of sodium alginate, reverse osmosis-infiltration cleaning frequency are 20min-60s, repeat to be checked afterwards for 24 hours, water flux is only
Restore to the 90.2% of initial flux, effluent index is COD=10mg/L, pH 7.5 at this time, can carry out reuse.
Embodiment 7 is reverse osmosis-processing waste water containing inorganic pollution
The waste water of sodium thiosulfate is mainly contained using the method processing of embodiment 2, condition is as follows: raw water SDI < 5, pH
It is 6.5, free cl concn is lower than 0.1ppm, and inflow temperature is 25 DEG C, conductivity 3.98ms/cm；Membrane module 2 selects Hydranautics
CPA3-LD antipollution bitter coiled reverse osmosis membrane, initial water flux are 46.9L/ (hm2), operating pressure 1.6MPa, across
Membrane pressure difference is lower than 0.1MPa；Oxygen flow is 0.13L/min, into the ozone/oxygen gas admixture of gas of air and liquid mixer 10,
Ozone concentration is 6mg/L；After air and liquid mixer 10 is to concentrated water processing, ozone concentration is lower than 2.5mg/L in gas-liquid mixture, can
To play certain bactericidal effect, and membrane material will not be made to deteriorate.Reverse osmosis produced water running 20min, water flux are reduced to initial logical
90.0% or so of amount starts to carry out infiltration cleaning, and scavenging period about 45s is wherein full of concentrated water and ozone mixture in pipeline
About time-consuming 5s or so, flux recovery are the 99.8% of initial flux；Repeat the stream of reverse osmosis-infiltration cleaning after cleaning
Journey.The waste water of sodium thiosulfate is mainly contained using the method processing of the present embodiment, reverse osmosis-infiltration cleaning frequency is 20min-
45s repeats to be checked afterwards for 24 hours, and water flux restores to the 96.1% of initial flux, and water outlet conductivity is 72 μ s/cm, pH
It is 7.3, reuse can be carried out.
Embodiment 8 is reverse osmosis-processing waste water containing inorganic pollution
The waste water of sodium thiosulfate is mainly contained using the method processing of embodiment 3, experiment condition is same as Example 7.
Bipolar membrane module is increased under same experimental conditions, in the present embodiment, using acid solution to the inorganic dirt in reverse osmosis membrane assembly
Dye object carries out infiltration cleaning, and first sub-percolation cleaning can be such that the water flux of film restores to 99.8% or more；It is clear to repeat reverse osmosis-infiltration
It washes the period (20min-45s) to be checked afterwards for 24 hours, water flux can restore to the 99.4% of initial flux, at this point, effluent index is
COD=5mg/L, pH 7.3 can carry out reuse.
9 nanofiltrations of embodiment-processing contains organic pollutant wastewater
The waste water of sodium alginate is mainly contained using the method processing of embodiment 2, condition is as follows: raw water SDI < 5, COD=
50mg/L, pH 6.5, free cl concn are lower than 0.1ppm, and inflow temperature is 25 DEG C；Membrane module 2 selects Hydranautics HNF90-
4040 rolling nanofiltration membranes, initial water flux are 42.9L/ (hm2), operating pressure 0.7MPa, transmembrane pressure is lower than 0.1MPa；
Oxygen flow is 0.25L/min, into the ozone/oxygen gas admixture of gas of air and liquid mixer 10, ozone concentration 12mg/L；
After handling in air and liquid mixer concentrated water, ozone concentration is lower than 5mg/L in gas-liquid mixture, can play certain sterilization and make
With, and membrane material will not be made to deteriorate.Nanofiltration produces water running 20min, and water flux is reduced to 87.0% of initial flux or so, starts
Infiltration cleaning is carried out, scavenging period about 60s is wherein full of concentrated water and ozone mixture about time-consuming 5s or so in pipeline, flux is extensive
It is again the 99.6% of initial flux；Repeat nanofiltration-infiltration cleaning process after cleaning.Using the method for the present embodiment
Processing mainly contains the waste water of sodium alginate, and nanofiltration-infiltration cleaning frequency is 20min-60s, repeats to be examined afterwards for 24 hours
It looks into, water flux restores to the 98.6% of initial flux, and effluent index is COD=5mg/L at this time, and pH 7.4 can be returned
With.
10 nanofiltrations of embodiment-processing waste water containing inorganic pollution
The waste water of sodium thiosulfate is mainly contained using the method processing of embodiment 2, condition is as follows: raw water SDI < 5, pH
It is 6.5, free cl concn is lower than 0.1ppm, and inflow temperature is 25 DEG C, conductivity 3.98ms/cm；Membrane module 2 selects Hydranautics
HNF90-4040 rolling nanofiltration membrane, initial water flux are 42.9L/ (hm2), operating pressure 0.7MPa, transmembrane pressure is lower than
0.1MPa；Oxygen flow is 0.13L/min, and into the ozone/oxygen gas admixture of gas of air and liquid mixer 10, ozone concentration is
6mg/L；After handling in air and liquid mixer 10 concentrated water, ozone concentration is lower than 2.5mg/L in gas-liquid mixture, can play one
Determine bactericidal effect, and membrane material will not be made to deteriorate.Nanofiltration produces water running 20min, and water flux is reduced to the 90.2% of initial flux
Left and right starts to carry out infiltration cleaning, and scavenging period about 60s is wherein left full of concentrated water and ozone mixture about time-consuming 5s in pipeline
The right side, flux recovery are the 99.9% of initial flux；Repeat nanofiltration-infiltration cleaning process after cleaning.Using this reality
The method processing for applying example mainly contains the waste water of sodium thiosulfate, and nanofiltration-infiltration cleaning frequency is 20min-60s, is repeated
It is checked afterwards for 24 hours, water flux restores to the 99.2% of initial flux, and water outlet conductivity is 83 μ s/cm, pH 7.2 at this time, can
To carry out reuse.
Claims (10)
1. a kind of method of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, includes the following steps:
A, the concentrated water for generating reverse osmosis/nanofiltration system is collected in concentrated water tank, is produced water and is collected in producing water pot；
B, close reverse osmosis/nanofiltration system inlet valve and produce water outlet valve, reduce freq uency conversion supercharging pump pressure, make it is reverse osmosis/
The process of osmosis opposite with when production water running process occurs in nanofiltration membrane component；
C, the concentrated water in the step a concentrated water tank is sent into air and liquid mixer, ozone is added in Xiang Suoshu air and liquid mixer, it is dense
Water and ozone are sufficiently mixed in the air and liquid mixer；
D, it will obtain passing through the freq uency conversion supercharging through catalytic ozonation treated concentrated water in air and liquid mixer in the step c
It being pumped into the reverse osmosis/nanofiltration membrane component, the production water produced in water pot enters in the reverse osmosis/nanofiltration membrane component,
The process of osmosis contrary with when production water running occurs, realizes the on-line cleaning to reverse osmosis/nanofiltration membrane.
2. the method for concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as described in claim 1, wherein described
Step c is that the concentrated water in the step a concentrated water tank is sent into bipolar membrane module, and the acid solution of generation enters in acid storage tank, is generated
Lye enter storage alkali tank in, when reverse osmosis/nanofiltration membrane system processing water inlet in major pollutants be inorganic pollution when, will
Acid solution in the acid storage tank is mixed with the salting liquid obtained after the bipolar film process, and being mixed into Bipolar Membrane, treated
Concentrated water is sent into air and liquid mixer, is added ozone in Xiang Suoshu air and liquid mixer, and Bipolar Membrane treated concentrated water and ozone are in institute
It states in air and liquid mixer and is sufficiently mixed.
3. the method for concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as described in claim 1, wherein described
Step c is that the concentrated water in the step a concentrated water tank is sent into bipolar membrane module, and the acid solution of generation enters in acid storage tank, is generated
Lye enter storage alkali tank in, when reverse osmosis/nanofiltration membrane system processing water inlet in major pollutants be organic pollutant when, will
Lye in the storage alkali tank is mixed with the salting liquid obtained after the bipolar film process, and being mixed into Bipolar Membrane, treated
Concentrated water is sent into air and liquid mixer, is added ozone in Xiang Suoshu air and liquid mixer, and Bipolar Membrane treated concentrated water and ozone are in institute
It states in air and liquid mixer and is sufficiently mixed.
4. the method for concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as described in claim 1, wherein described
After reverse osmosis/nanofiltration system produces water running 10-30 minutes, closes inlet valve and produce water outlet valve, reduce the pressure of freq uency conversion supercharging pump
Power carries out online infiltration cleaning reverse osmosis/nanofiltration membrane 30-300 seconds.
5. a kind of device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane, which includes that freq uency conversion supercharging pumps, is anti-
Infiltration/nanofiltration membrane component produces water pot, concentrated water tank, air and liquid mixer and ozone generator, the outlet of the freq uency conversion supercharging pump and institute
The water inlet connection of membrane module is stated, the production mouth of a river of the membrane module is connect with the production water pot, the concentrated water outlet of the membrane module
It is connect with the concentrated water tank water inlet, the concentrated water tank concentrated water outlet is connect with the air and liquid mixer inlet, the gas-liquid
Mixer air inlet is connect with the ozone generator, and the air and liquid mixer outlet is connected with freq uency conversion supercharging pump.
6. the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein described
Device further includes bipolar membrane module, and the bipolar membrane module setting is in concentrated water tank concentrated water outlet and the air and liquid mixer feed liquor
Between mouthful, the salting liquid outlet of the bipolar membrane module is connect with the air and liquid mixer inlet, the bipolar membrane module
Acid solution outlet is connect by acid solution outlet valve with the air and liquid mixer inlet, and the lye export of the bipolar membrane module passes through
Lye export valve is connect with the air and liquid mixer inlet.
7. the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as claimed in claim 6, wherein the dress
It sets and further includes acid storage tank and connected with storage alkali tank, the acid solution outlet of the acid storage tank and the bipolar membrane module, the storage alkali tank
It is connect with the lye export of the bipolar membrane module.
8. the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein described
Reverse osmosis/nanofiltration membrane component is rolled film or plate membrane.
9. the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein described
Salt mouth is thrown in setting on concentrated water tank.
10. the device of concentrated water catalytic ozonation on-line cleaning reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein the dress
Setting further includes pre-processing assembly, and the upstream of the freq uency conversion supercharging pump is arranged in the pre-processing assembly.
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