CN109562962A - Membrane filtering method and membrane filtration system - Google Patents
Membrane filtering method and membrane filtration system Download PDFInfo
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- CN109562962A CN109562962A CN201780046662.4A CN201780046662A CN109562962A CN 109562962 A CN109562962 A CN 109562962A CN 201780046662 A CN201780046662 A CN 201780046662A CN 109562962 A CN109562962 A CN 109562962A
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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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
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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
- B01D61/58—Multistep processes
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
Abstract
According to one of the present embodiment mode, provide a kind of membrane filtering method, comprising: which coagulating agent is added into processing water, the processing water is prepared and flocculant is added into water to be processed and carries out flocculation and settlement treatment or flocculation and dissolved air floatation processing；Then film filtration treatment, such as ultrafiltration membrane treatment and/or secondary filter film process are carried out.
Description
Technical field
The present invention relates to membrane filtering methods and membrane filtration system.
Background technique
In general, flocculant is added in water to be processed to carry out flocculation with what settlement treatment or dissolved air floatation were handled and give up
Water process is known (for example, with reference to patent document 1).
Quotation list
Patent document
Patent document 1:JPH11-57313A
Summary of the invention
Technical problem
However, if carrying out flocculation and settlement treatment or dissolved air floatation processing and the processing of preparation to by using flocculant
Water uses ultrafiltration membrane or microfiltration membranes, then it some times happens that a kind of phenomenon (pollution), wherein the surface of film is contaminated, and fenestra quilt
Blocking.Therefore, the purpose of the present invention is to provide a kind of membrane filtering method and membrane filtration systems, are able to suppress ultrafiltration membrane or micro-filtration
The pollution of film, and work as and carry out flocculation and settlement treatment or dissolved air floatation processing and the processing water of preparation with by using flocculant
It can be realized stable operation when being used together.
Solution to problem
(1) embodiment of the present invention is membrane filtering method on one side comprising: coagulating agent is added into processing water,
The processing water is by the way that flocculant is added into pending water and carries out at flocculation and settlement treatment or flocculation and dissolved air floatation
Reason and prepare；With progress at least one of ultrafiltration membrane treatment and micro-filtration film process film filtration treatment.
(2) in the membrane filtering method described in above-mentioned (1), wherein when carrying out the film filtration treatment, preferably carry out pair
The processing water applies shearing force and adds at least one of oxidant into the processing water, so that flocculant in processing water
Average molecular weight no more than film used in film filtration treatment molecular cut off.
(3) in the membrane filtering method described in above-mentioned (1) or (2), the additive amount of the coagulating agent is preferably described wait locate
0.5 times to 75 times for managing the concentration (mg/L) of the flocculant in water.
(4) in the membrane filtering method described in any one of above-mentioned (1)-(3), preferably by flocculation and settlement treatment
Or flocculation controls coagulating agent by the concentration of the LC-OCD polymerized organics detected in the processing water of dissolved air floatation processing
Additive amount.
(5) in the membrane filtering method described in any one of above-mentioned (1)-(4), preferably to the place Jing Guo film filtration treatment
It manages water and carries out the post-processing of at least one of active carbon processing and reverse osmosis membrane processing.
(6) excellent when carrying out the film filtration treatment in the membrane filtering method described in any one of above-mentioned (1)-(5)
Selection of land controls the pH of the processing water, so that bright lattice Lear (Langelier) saturation index (LSI) of the processing water is less than 0.
(7) one embodiment of the invention is a kind of membrane filtration system on one side comprising: coagulating agent addition is single
Member, for adding coagulating agent into processing water, the processing water is by the way that flocculant is added into pending water and flocculates
It is prepared with settlement treatment or flocculation with dissolved air floatation processing；And
Film filtration treatment unit has at least one of ultrafiltration membrane and microfiltration membranes, and to the processing water for being added with coagulating agent
Carry out film filtration treatment.
(8) membrane filtration system described in above-mentioned (7) preferably includes: the shearing force for applying shearing force to processing water is applied
Add unit and at least one of the oxidant adding unit for adding oxidant into processing water in film filtration treatment,
Middle at least one of the shearing force and addition oxidant of applying ensures to handle the average molecular weight of the flocculant in water no more than film
The molecular cut off of film used in filtration treatment.
(9) in the membrane filtration system described in above-mentioned (7) or (8), the additive amount of the coagulating agent is preferably described wait locate
0.5 times to 75 times for managing the concentration (mg/L) of the flocculant in water.
(10) membrane filtration system as described in any one of above-mentioned (7)-(9) preferably has post-processing unit, for warp
The processing water for crossing film filtration treatment is post-processed, wherein
The post-processing unit is preferably at least one of active carbon processing unit and reverse osmosis membrane processing unit.
(11) membrane filtration system as described in any one of above-mentioned (7)-(10) preferably includes pH control unit, the pH
Control unit is used to control the pH of the processing water, so that when carrying out the film filtration treatment, so that the processing water is bright
Lattice Lear saturation index (LSI) is less than 0.
Advantageous effect of the invention
Membrane filtering method and membrane filtration system according to embodiments of the present invention are worked as to be flocculated with by using flocculant
When being used together with the processing water that settlement treatment or dissolved air floatation are handled and prepared, it is able to suppress and pollutes and can be realized ultrafiltration
The stable operation of film or microfiltration membranes.
Detailed description of the invention
Fig. 1 is the schematic diagram for showing an example of structure for processing system according to an embodiment of the invention.
Fig. 2 is the schematic diagram for showing an example of structure for processing system according to another embodiment of the invention.
Fig. 3 is the schematic diagram for showing an example of structure for processing system according to another embodiment of the invention.
Fig. 4 is the schematic diagram for showing an example of structure for processing system according to another embodiment of the invention.
Fig. 5 is the schematic diagram for showing an example of structure for processing system according to another embodiment of the invention.
Fig. 6 is the schematic diagram for showing the structure of the processing system in reference example.
Fig. 7 is to indicate the filtration resistance (1/m) of example 1 and 2 and the film filter in comparative example 1 and 2 relative to filtering body
Product (m3/m2) result figure.
Fig. 8 is to indicate the filtration resistance (1/m) of the film filter of example 3 and comparative example 3 relative to filtration volume (m3/m2)
As a result figure.
Fig. 9 is to indicate the filtration resistance (1/m) of the film filter of example 4 and comparative example 4 relative to filtration volume (m3/m2)
As a result figure.
Specific embodiment
Embodiment of the present invention is described below.These embodiments are only to realize example of the invention, and the present invention is exhausted
It is not restricted by the embodiments.
Fig. 1 is the schematic diagram of an example of the structure for the processing system for showing embodiment according to the present invention.Fig. 1 institute
The processing system 1 shown includes flocculating setting system and membrane filtration system.Flocculating setting system includes the first flocculation reaction tank 10, wadding
Solidifying agent addition pipeline 12 and flocculating setting tank 14.Membrane filtration system includes the coagulating agent as one example of coagulating agent adding unit
Adding set 15 and coagulating agent add pipeline 16, the second flocculation reaction tank 18 and as one examples of film filtration treatment unit
Film filter 20.
Water pipeline 22 to be processed is connected to the entrance of the first flocculation reaction tank 10.In addition, one end of connecting pipeline 24a connects
It is connected to the outlet of the first flocculation reaction tank 10, the other end is connected to the entrance of flocculating setting tank 14, and one end of connecting pipeline 24b connects
It is connected to the outlet of flocculating setting tank 14, the other end is connected to the entrance of the second flocculation reaction tank 18, and the one of connecting pipeline 24c
End is connected to the outlet of the second flocculation reaction tank 18, and the other end is connected to the entrance of film filter 20.In addition, film filter
20 outlet is connected to processing water pipeline 26.Flocculant addition pipeline 12 is connected to the first flocculation reaction tank 10.In addition, coagulating agent
One end of addition pipeline 16 is connected to coagulating agent adding set 15, and the other end is connected to the second flocculation reaction tank 18.
Coagulating agent adding set 15 is made of the tank of receiving coagulating agent, the pump of discharge coagulating agent and valve etc..Add from coagulating agent
The coagulating agent that feeder apparatus 15 is supplied passes through coagulating agent addition pipeline 16 and is supplied to the second flocculation reaction tank 18.The present embodiment
Used in the example of coagulating agent include polyaluminium chloride (PACL), aluminum sulfate, iron chloride, ferric sulfate and aluminium chloride.
The example of flocculant for the present embodiment includes polymer flocculants such as polyacrylamide flocculant, polysulfonate
Acids flocculant, polyacrylic flocculant, polyacrylate flocculant, polyamines flocculant and polymethacrylic acid wadding
Flocculant (coagulating agent) such as surfactant of solidifying agent and small-molecular-weight.Flocculant (such as by flocculant not shown in the figure
Adding set supply) flocculant addition pipeline 12 is passed through, and supply the first flocculation reaction tank 10.
Film filter 20 includes at least one in the UF film device with ultrafiltration membrane and the MF film device with microfiltration membranes
It is a.UF film device or MF film device are for example made of at least one module, which, which has, is contained in surpassing in resealable container
Filter membrane or microfiltration membranes.The shape of ultrafiltration membrane or microfiltration membranes is not particularly limited, possible shape includes hollow-fibre membrane, tubulose
Film, flat membrane and spiral membrane.Method for passing water through film filter 20 can be using any method of supplying water, including inner pressed
Method and external-compression type method, and any filter method, including cross-flow filtration and dead-end filtration can be applied.
The example of ultrafiltration membrane or the material of microfiltration membranes includes organic film such as polyvinylidene fluoride (PVDF), polyvinyl chloride
(PVC), polyether sulfone (PES) and cellulose acetate (CA) and inoranic membrane such as ceramics.
The molecular cut off of ultrafiltration membrane for example usually in the range of 5,000 to 360,000, and preferably 10,000 to
In the range of 360,000.The aperture of ultrafiltration membrane for example in the range of 0.01 μm to 0.1 μm, and preferably at 0.01 μm extremely
In the range of 0.03 μm.The aperture of microfiltration membranes is for example in the range of 0.1 μm to 0.5 μm, and preferably at 0.1 μm to 0.2 μm
In the range of.
The water to be processed handled by processing system 1 is not particularly limited, and example includes (such as outstanding containing impurity
Floating solid) and composition of scale (such as calcium) raw water, and the specific example of water to be processed include industrial wastewater (such as from
The waste water of electroplating system etc.), tap water, underground water (such as well water, spring and river bed water) and surface water be (for example, river water and lake
Water).
One example of the operation of the processing system 1 of the present embodiment is described below.
Water to be processed passes through water pipeline 22 to be processed and supplies the first flocculation reaction tank 10, and flocculant is from flocculant
It adds pipeline 12 and supplies the first flocculation reaction tank 10.In the first flocculation reaction tank 10, water to be processed is stirred with blender 28a
And flocculant, the impurity (such as suspended solid) in water to be processed flocculate.Then, the water to be processed containing flocculant is worn
It crosses connecting pipeline 24a and supplies flocculating setting tank 14, and flocculated impurity (such as suspended solid) is made to be precipitated as sludge.
Supernatant passes through connecting pipeline 24b and supplies the second flocculation reaction as the processing water by flocculating setting processing
Tank 18.In addition, coagulating agent, which passes through coagulating agent addition pipeline 16 from coagulating agent adding set 15, is supplied to the second flocculation reaction tank 18.
In the second flocculation reaction tank 18, with blender 28b stir process water and coagulating agent, make to handle any remaining flocculant in water
It is contacted with coagulating agent.Pass through connecting pipeline 24c containing the processing water for being added to coagulating agent and is introduced into film filter 20.Place
The impurity managed in water is retained by such as ultrafiltration membrane of the filter membrane in film filter 20 or microfiltration membranes, has removed the processing water of impurity from
Water pipeline 26 is managed to be discharged.By the processing water being achieved in that for example may be used as food processing factory, chemical plant, semiconductor factory and
Washing water etc. in machine works etc..
Using the regular backwash film filter 20 of the processing water obtained from film filtration treatment etc., on the surface of the film miscellaneous is gathered
Matter in system perhaps together with backwash waste from being discharged or be admitted in flocculate settling tank 14.With regard to realizing in backwash waste
Suspended solid sedimentation and separation for, and just improve the water rate of recovery (processing water/water supply ratio, if waste water
It is discharged from system, the water rate of recovery can reduce) for, backwash waste is preferably fed in flocculating setting tank 14.
In general, flocculating if carrying out film filtration treatment to the processing water containing flocculant with ultrafiltration membrane or microfiltration membranes etc.
Agent is gathered on the surface of the film, and is easy to happen the pollution of film.However, in the present embodiment, it is believed that by make coagulating agent with
Flocculant contact, coagulating agent adhere on flocculant, convert flocculant to the form being less likely to adhere in film surface, or
Person can be by way of backwash etc. be easy from film surface disengaging.Therefore, film filtering is carried out in the case where not adding coagulating agent
The case where processing, is compared, and then carries out film filtration treatment by addition coagulating agent, can inhibit the pollution of film, and may be implemented
More stable operation.However, although it is contemplated that such system, wherein using flocculant flocculation and the settlement treatment phase
Between, coagulating agent is added together with flocculant, still, though in this type of system, also have a certain amount of flocculant (such as
It is not condensed the flocculant of agent adherency) remain in the processing water handled by flocculating setting, therefore added with by coagulating agent
Into the processing water by flocculating setting processing, the method for then carrying out the present embodiment of film filtration treatment is compared, it more difficult to be obtained
It obtains satisfactory fouling membrane to inhibit, realizes that stable processing is also more difficult.
The additive amount of coagulating agent is not particularly limited, condition is that it can inhibit fouling membrane, but for example, coagulating agent
In the range of measuring 0.5 times to 75 times of the concentration of flocculant preferably in handling water (mg/L), come from the viewpoint of economic feasibility
It sees, more preferably in the range of 0.5 times to 2.5 times of amount.If the additive amount of coagulating agent is less than 0.5 times, then it is assumed that may not
Fouling membrane can satisfactorily be inhibited, and if amount is more than 75 times, then it is assumed that it is filtered caused by the flocculate as derived from coagulating agent
Resistance can increase.Therefore, compared with the case where being unsatisfactory for the amount of above range, it is ensured that the amount met the above range can more have
Effect ground inhibits fouling membrane.
In the present embodiment, to use flocculant by flocculation and settlement treatment obtain processing water be described,
But similar effect can also be obtained for using the flocculation of flocculant to handle the processing water obtained with dissolved air floatation.Flocculation and
Dissolved air floatation processing can be such as conventionally known dissolved air floatation processing (for example, see JP5239653B).
For improving the contact rate between flocculant and coagulating agent, flocculation reaction tank is preferably provided (the shown in Fig. 1
Two flocculation reaction tanks 18), but for reducing installation space etc., processing system is as shown in Figure 2, flocculates without setting
Reactor tank, and coagulating agent addition pipeline 16 is mounted on connecting pipeline 24b, can also carry out pipeline note using by coagulating agent
Enter.
Fig. 3 is the schematic diagram for showing an example of structure for the processing system according to another embodiment.In Fig. 3 institute
In the processing system 3 shown, those structures identical with processing system 1 shown in Fig. 1 are marked using identical appended drawing reference
Note, and omit the description to these structures.Processing system 3 shown in Fig. 3 is configured such that so that carrying out film filtration treatment
When, oxidant is added in the processing water for handling (or flocculation and dissolved air floatation processing) by flocculating setting.Specifically, figure
Processing system 3 shown in 3 includes oxidant adding set 29 and oxidant the addition pipeline 30 as oxidant adding unit, oxygen
Agent passes through oxidant from oxidant adding set 29 and adds pipeline 30, and is added in the second flocculation reaction tank 18.Oxidant
It can also be carried out by way of pipeline shown in Fig. 2 injects.
In the case where using polymer flocculants for example polyacrylamide base flocculant being as flocculant, flocculant is averaged
Molecular weight (weight average molecular weight or number-average molecular weight) is typically larger than the flocculant of the ultrafiltration membrane that follow-up phase uses or microfiltration membranes
Molecular cut off.If molecular weight is more than that the flocculant of retaining molecular weight remains in processing water, flocculant is to fouling membrane
Have an impact.Molecular cut off is confirmed as corresponding to 90% rejection when providing the standard substance with known molecular amount to film
Molecular weight, for example, if being supplied to molecular cut off containing the processing water of polymer flocculants that molecular weight is more than 5,000
Ultrafiltration membrane or the microfiltration membranes for being 5,000, then at least 90% polymer flocculants capture envelope.
Therefore, in processing system 3 shown in Fig. 3, by oxidant being added in film filtration treatment in processing water,
The strand of flocculant is cleaved, and the molecular weight of flocculant is reduced to not higher than ultrafiltration membrane or the molecular cut off of microfiltration membranes
Value, the preferably smaller than value of molecular cut off.As a result, a part of flocculant does not have envelope capture, then flocculant and processing water one
It rises through film, therefore compared with the situation for only adding coagulating agent, can preferably inhibit fouling membrane.
The example of oxidant includes hypochlorous alkali metal salt such as sodium hypochlorite and postassium hypochlorite, hypochlorous alkaline-earth metal
Salt such as calcium hypochlorite and barium hypochlorite, chlorous alkali metal salt such as lithium chlorite, sodium chlorite and potassium chlorite are chlorous
Alkali salt such as calcium chlorite, barium chlorite, other chlorous metal salts such as chlorous acid nickel, the alkali metal salt of chloric acid such as chlorine
Sour ammonium, sodium chlorate, the alkali salt of chloric acid such as calcium chlorate.
The additive amount of oxidant is not particularly limited, as long as the molecular weight of flocculant can be reduced to not higher than film by it
Molecular cut off value, but in the water to be processed before being flocculated and being settled flocculant concentration (mg/L) oxidation
The amount of agent is preferably in the range of 0.5 times to 75 times, more preferably in the range of 0.5 times to 2.5 times.
In addition, the additive amount of coagulating agent is preferably according to LC-OCD by flocculating setting processing or flocculation treatment or molten air bearing
The polymerized organics concentration detected in the processing of processing is selected to control.LC-OCD be it is a kind of according to molecular weight to organic matter carry out
The technology of fractionation, in terms of retention time, display polymerized organics, humus, humus catabolite, low molecular weight are organic
The peak value of acid and low-molecular-weight organic matter etc., the corresponding concentration of each peak value can quantify.
Think that polymerized organics matter facilitates film blocking, therefore by being determined in detail by flocculating setting processing or flocculation
Polymerized organics concentration in reason and the processing Organic substance in water of dissolved air floatation processing, the amount of coagulating agent addition can be set as more
Suitable amount.The addition of coagulating agent is increased or decreased by the size of the peak value of the polymerized organics detected according to LC-OCD
Amount, can reduce operating cost.
Other than adding oxidant, the other methods for reducing flocculating agent molecule amount include applying shearing to processing water
The method of power.The blender 28b being arranged in the second flocculation reaction tank 18 is the example of shearing force applying unit, and by stirring
It mixes processing water and applies shearing force, the strand of flocculant can be cleaved, and the molecular weight of flocculant is reduced to not higher than super
The value of filter membrane or the molecular cut off of microfiltration membranes.For example, by adjusting mixing speed and mixing time etc., it can be by flocculant
Molecular weight is reduced to the value of the molecular cut off not higher than ultrafiltration membrane or microfiltration membranes.For reducing the stirring speed of flocculating agent molecule amount
Degree is for example generally set in the range of 200rpm to 1,000rpm, preferably in the range of 700rpm to 1,000rpm.In addition,
For reducing flocculating agent molecule amount mixing time for example usually in the range of 5 minutes to 1 hour, preferably at 30 minutes to 1
In the range of hour.
Fig. 4 is the schematic diagram for showing an example of structure for the processing system according to another embodiment.In Fig. 4 institute
In the processing system 4 shown, those structures identical with processing system 1 shown in Fig. 1 are marked using identical appended drawing reference
Note, and omit the description to these structures.Processing system 4 shown in Fig. 4 includes the activated-carbon device 32 filled with active carbon
The reverse osmosis membrane apparatus 34 of reverse osmosis membrane is provided with the follow-up phase in film filter 20.Handle one end of water pipeline 26a
It is connected to the exit of film filter 20, the other end is connected to the entrance of activated-carbon device 32.In addition, processing water pipeline 26b
One end be connected to the outlet of activated-carbon device 32, the other end is connected to the entrance of reverse osmosis membrane apparatus 34.Pipeline 36 is permeated to connect
It is connected to the permeant outlet of reverse osmosis membrane apparatus 34, concentrate pipeline 38 is connected to concentrate outlet.
Reverse osmosis membrane used in the present embodiment is the film that can remove the ion component in processing water, and further includes
Nanofiltration membrane (NF).The shape of reverse osmosis membrane is not particularly limited, possible shape includes hollow-fibre membrane, tubular film, flat membrane
And spiral membrane.The example of the material of reverse osmosis membrane includes polyamide polymer, piperazine acidamide material and cellulose acetate class material
Material.
In processing system shown in Fig. 4, the processing water being discharged from film filter 20 passes through processing water pipeline 26a, and
Supply activated-carbon device 32.After removing the impurity in processing water by activated-carbon device 32, water is handled from processing water pipeline
26b is supplied to reverse osmosis membrane apparatus 34, and is separated into penetrant and concentrate.The penetrant obtained from reverse osmosis membrane apparatus 34
(processing water) is discharged from penetrant pipeline 36.The penetrant being achieved in that serves not only as food processing factory, chemical plant, partly leads
Washing water etc. in body factory and machinery plant etc., and may be used as dilution water, drinking water, recirculated water, air conditioning water, be used for
Raw water, flusher raw water and the steam industrial water etc. of pure water production.From the concentrate that reverse osmosis membrane apparatus 34 obtains from concentration
Property management line 38 is discharged, and can for example be stored in holding vessel not shown in the figure.
Processing system shown in Fig. 4 is equipped with activated-carbon device 32 and reverse osmosis membrane apparatus 34, but according to for final place
The target water quality etc. for managing water can choose whether only to install activated-carbon device 32, only install reverse osmosis membrane apparatus 34 or simultaneously
Activated-carbon device 32 and reverse osmosis membrane apparatus 34 are installed.Although being omitted from description related with attached drawing, activated-carbon device
32 and/or reverse osmosis membrane apparatus 34 also may be mounted in Fig. 2 and processing system shown in Fig. 3.
Fig. 5 is the schematic diagram for showing an example of structure for processing system according to another embodiment of the invention.
In processing system 5 shown in Fig. 5, those structures identical with processing system 1 shown in Fig. 1 use identical appended drawing reference
It is marked, and omits the description to these structures.Processing system 5 shown in Fig. 5 includes one as pH control unit
The pH control system of example.There is pH control system pH adjusting agent adding set 40, pH adjusting agent to add pipeline 42, water quality detection
Device 44 and control unit 46.
PH adjusting agent adding set 40 for example by the tank for storing pH adjusting agent, the pump for pH adjusting agent to be discharged and
The composition such as valve.One end of pH adjusting agent addition pipeline 42 is connect with pH adjusting agent adding set 40, and the other end and the second flocculation are anti-
Tank 18 is answered to connect.
Water quality detecting device 44 has pH sensor, temperature sensor, conductivity sensor, calcium hardness sensor and total
Alkalinity sensor, and detect pH value, water temperature, conductivity, calcium hardness and the total alkalinity of the processing water in the second flocculation reaction tank 18.
Control unit 46 includes processor and memory, and there is the bright lattice Lear saturation index as functional block to calculate
Part 48 and pH adjusting agent amount control section 50.Bright lattice Lear is entered by the various detected values that water quality detecting device 44 detects to satisfy
With index calculating section 48.Based on the bright lattice Lear saturation index calculated by bright lattice Lear saturation index calculating section 48, pH tune
Section dosage control section 50 calculates the amount of pH adjusting agent to be added, and controls the pH added by pH adjusting agent adding set 40
The amount of regulator.
The processor of control unit 46 executes various processing according to processing routine stored in memory, such as based on
Calculate the processing of bright lattice Lear saturation exponent and the processing of the additive amount for controlling pH adjusting agent.Control unit 46 is described below
Operation an example.
Bright lattice Lear saturation index calculating section 48 is based on the detected value calculation processing water detected by water quality detecting device 44
Bright lattice Lear saturation index.Bright lattice Lear saturation index (LSI) calculates generally according to following formula (1).
LSI=pH-pHs (1)
In formula (1), pH indicates the pH value of processing water.In addition, pHs value indicates to be in balance when the calcium carbonate in processing water
Theoretical pH value when both not dissolving or not precipitating when state, and calculated by following formula (2).
PHs=9.3+A value+B value-C value-D value (2)
In formula (2), A value is the corrected value determined by evaporation residue concentration.Evaporation residue concentration and conductivity phase
It closes, therefore defined conversion formula can be used by Conductivity Calculation evaporation residue concentration.B value is the correction determined by water temperature
Value.C value is the corrected value determined by calcium hardness.D value is the corrected value determined by total alkalinity.Relational expression or reference number can be used
It is worth table, determines A to D value from the detected value of water quality detecting device 44.
Bright lattice Lear saturation exponent is the general indicator that trend is formed for assessing scale in water system, for positive value,
Biggish absolute value representation calcium carbonate is easier to precipitate, and for negative value, absolute value is larger to show that calcium carbonate is less likely precipitating.
In addition, equilibrium state is realized when bright lattice Lear saturation index is 0, wherein the precipitating of calcium carbonate neither occurs nor carbon occurs
The dissolution of sour calcium.Based on these definition, when handling the bright lattice Lear saturation index of water less than 0, be less likely in ultrafiltration membrane or
Form the scale as caused by calcium carbonate in the film surface of microfiltration membranes, and on the contrary, when bright lattice Lear saturation index if it exceeds 0,
The scale as caused by calcium carbonate may be then formed on the surface of the film.
Therefore, when the bright lattice Lear saturation index of calculated processing water is 0 or bigger, pH adjusting agent amount control section
The amount of 50 setting pH adjusting agents to be added, so that the bright lattice Lear saturation index for handling water to be changed into the value less than 0.Then
PH adjusting agent is added in processing water by the amount of to be added pH adjusting agent of the pH adjusting agent adding set 40 based on the setting, from
And the bright lattice Lear saturation index for handling water is changed into the value less than 0.It such as can be clearly seen from formula (1), handle the bright of water
Lattice Lear saturation index is reduced with the reduction of the pH of processing water, is increased with the raising of pH.Therefore, it can be handled by adjusting
The pH of water handles the bright lattice Lear saturation index of water to control.
System of the processing system 5 of the present embodiment for example as processing fluoride waste is effective.Fluoride waste (to
The water of processing) flocculating setting processing or dissolved air floatation processing in, in order to recycle fluorine, calcium agent is added together with flocculant sometimes
Into water to be processed.Therefore, calcium can be contained sometimes from the processing water that this settlement treatment or dissolved air floatation processing obtain, handled
The bright lattice Lear saturation index of water may be 0 or higher.As a result, forming scale on ultrafiltration membrane or microfiltration membranes sometimes.But
In the present embodiment, as described above, making the bright lattice Lear saturation index of processing water (simultaneously less than 0 by the pH of control processing water
And become negative value), the generation of scale can be inhibited.Therefore, it can preferably inhibit fouling membrane, and may be implemented more stable
Operation.Although omitting from description related with attached drawing, pH control system also may be mounted at Fig. 2 to place shown in Fig. 4
In reason system.
(reference example)
Fig. 6 is the schematic diagram for showing the structure of the processing system in reference example.In processing system 6 shown in Fig. 6, those with
The identical structure of processing system 1 shown in Fig. 1 is marked using identical appended drawing reference, and is omitted and retouched to these structures
It states.Coagulating agent is not added to by wadding in this way, make when carrying out film filtration treatment by processing system 6 shown in Fig. 6
In the processing water of solidifying settlement treatment (or flocculation and dissolved air floatation processing), but oxidant is led to from addition oxidant device 29
Peroxide agent adding tube line 30 is added in the second flocculation reaction tank 18.The addition of oxidant can also be by shown in Fig. 2
The form of pipeline injection carries out.
In processing system shown in Fig. 6, by oxidant being added in film filtration treatment in processing water, flocculant
Strand be cleaved, the molecular weight of flocculant is reduced to a value of the molecular cut off not higher than ultrafiltration membrane or microfiltration membranes,
The preferably less than value of molecular cut off.As a result, a part of flocculant does not have envelope capture, then flocculant is together with processing water
By film, therefore compared with the situation for only adding coagulating agent, it can preferably inhibit fouling membrane.
The additive amount of oxidant is not particularly limited, as long as the molecular weight of flocculant can be reduced to not higher than film by it
Molecular cut off value, but handle water oxygen agent amount preferably at 2.5 times to 100 times of the concentration of flocculant (mg/L)
In the range of, more preferably in the range of 20 times to 50 times.
Other than adding oxidant, the other methods for reducing flocculating agent molecule amount include applying shearing to processing water
The method of power.The blender 28b being arranged in the second flocculation reaction tank 18 is the example of shearing force applying unit, and by stirring
It mixes processing water and applies shearing force, the strand of flocculant can be cleaved, and the molecular weight of flocculant is reduced to not higher than super
The value of filter membrane or the molecular cut off of microfiltration membranes.Mixing speed for reducing flocculating agent molecule amount is for example generally set to
In the range of 200rpm to 1,000rpm, preferably in the range of 700rpm to 1,000rpm.In addition, for reducing flocculant point
The mixing time of son amount is for example usually in the range of 5 minutes to 1 hour, preferably in the range of 30 minutes to 1 hour.Although
It is omitted from description related with attached drawing, but processing system shown in fig. 6 also can be applied to processing shown in Fig. 2 to Fig. 5
System.
Example
The present invention will be described in more detail for a series of embodiments used below and comparative example, but the present invention is never by following implementation
The limitation of example.
(example 1)
The electroplating system waste water with water quality shown in table 1 is handled using processing system shown in Fig. 1.
[table 1]
| Electroplating system waste water | |
| pH | 9.5 |
| TOC(mg/L) | 0.97 |
| Fe(mg/L) | 204 |
UF film device is used as the film filter of example 1.The details of UF film device is as follows.
Size: outer diameter: 230mm × height: 2,400mm
Filter table area (film surface product): 77m2
Ultrafiltration membrane: the hollow-fibre membrane made of PVDF, normal pore size: 0.01 μm of (nominal retention: 360,000Da)
Filter method: external pressure dead-end filtration
Handle flow: 9.6m3/h
Have to addition and the conduct of 1.0ppm polyacrylamide polymer is added in the electroplating system waste water of water quality shown in table 1
Supernatant after carrying out flocculating setting processing, is supplied the second flocculation reaction tank by flocculant.It is added into the second flocculation reaction tank
After 75ppm iron chloride is as coagulating agent, water is supplied into film filter (UF film device), carries out film filtration treatment.
(example 2)
Other than the amount of coagulating agent (iron chloride) is become 10ppm from 75ppm, processing identical with example 1 is carried out.
(comparative example 1)
Other than not adding coagulating agent (iron chloride), processing identical with example 1 is carried out.
(comparative example 2)
In addition to the amount of flocculant (polyacrylamide based polyalcohol) is become 0.5ppm from 1.0ppm, and coagulating agent (chlorine is not added
Change iron) except, carry out processing identical with example 1.
The water of the processing water obtained after the film filtration treatment in example 1 and example 2 and comparative example 1 and comparative example 2
Matter result is shown in Table 2.Fig. 7 shows the filtering of example 1 and example 2 and comparative example 1 and the film filter in comparative example 2
Resistance (1/m) is relative to filtration volume (m3/m2) result.
[table 2]
As shown in Figure 7, and wherein the ratio of film filtration treatment is carried out in the case where not adding coagulating agent into processing water
It is compared compared with example 1 with comparative example 2, before carrying out film filtration treatment, 1 He of example of coagulating agent is added into processing water obtained
Flocculation and settlement treatment of the example 2 by using flocculant can also inhibit any of filtration resistance even if filtration volume increases
Increase.The increase of filtration resistance shows the bad of the strainability as caused by fouling membrane relative to the increased ratio of filtration volume
Change.Therefore, the processing method of example 1 and example 2 is able to suppress fouling membrane and can be realized stable operation.In view of comparative example
The additive amount of flocculant is greater than the amount in comparative example 2 in 1, shows filtration resistance increment rate higher than comparative example 2, it may be said that residual
Flocculant processing water facilitate fouling membrane.On the other hand, in example 1 and example 2, although being added identical as comparative example 1
The flocculant of amount, also almost without the increase that filtration resistance occurs, shows that fouling membrane is pressed down even if filtration volume increases
System.It is thought that this is because coagulating agent, which is added, to be made to handle the flocculant in water and be converted into be less likely to adhere on the surface of the film
Form.
In addition, as shown in table 2, in example 1 and example 2, the TOC value for handling water is reduced, it was demonstrated that remaining flocculant is
It is processed.
(example 3)
In addition to the amount of flocculant (polyacrylamide polymer) is become 5.0ppm from 1.0ppm, and by coagulating agent (chlorination
Iron) amount become except 2.5ppm from 75ppm, carry out identical with example 1 processing.
(comparative example 3)
1ppm iron chloride is added to 5.0ppm polyacrylamide polymer together as flocculant as coagulating agent to be had
It in the electroplating system waste water of water quality shown in table 1, and is flocculating with after settlement treatment, is making supernatant directly through film filter
(above-mentioned UF film device) carries out film filtration treatment.
The results are shown in Table 3 for the water quality of the processing water obtained after film filtration treatment in example 3 and comparative example 3.
[table 3]
| Example 3 | Comparative example 3 | |
| pH | 5.9 | 5.9 |
| TOC(mg/L) | 0.81 | 0.84 |
| Fe(mg/L) | <0.05 | <0.05 |
Fig. 8 shows the filtration resistance (1/m) of example 3 and the film filter in comparative example 3 relative to filtration volume
(m3/m2) result.It is observed in the increment rate of filtration resistance in example 3 and example 1 and example 2 similar.In contrast,
The increment rate of filtration resistance in comparative example 3 is higher than the increment rate observed in example 3 (wherein the additive amount of coagulating agent is identical),
It but is below the case where observing in the comparative example 1 and 2 for being not added with coagulating agent.Based on these results, it may be said that in order to more preferable
Ground inhibits fouling membrane, it is necessary to which coagulating agent is added to the processing water for carrying out flocculation and settlement treatment by using flocculant and preparing
In.
(example 4)
In addition to coagulating agent is become polyaluminium chloride (PACL) from iron chloride, and additive amount is become except 50ppm from 75ppm,
Carry out processing identical with example 1.
(comparative example 4)
Other than changing raw water sample time, processing identical with comparative example 1 is carried out.
Fig. 9 shows the filtration resistance (1/m) of example 4 and the film filter in comparative example 4 relative to filtration volume
(m3/m2) result.In the example 4 (wherein PACL is used as coagulating agent) in the mode similar similar to example 1 to 3, even if working as
When filtration volume increases, filtration resistance is also almost without increase, and fouling membrane is inhibited.On the contrary, being condensed in no addition
In the comparative example 4 of agent, with the increase of filtration volume, filtration resistance increases.
(example 5 to 10)
Using processing system shown in Fig. 1, simulated wastewater is handled.Simulated wastewater, which contains, to be dispersed in tap water
10mg/L bentonite.Film filter is identical as UF film device used in example 1.
In example 5, by 1.0ppm polyacrylic polymer (OX-304 (cationic polymer), by Organo
Corporation manufacture) it is added in above-mentioned simulated wastewater as flocculant, flocculation and settlement treatment are carried out, then by supernatant
Liquid supplies in the second flocculation reaction tank.After the PACL as coagulating agent of 10ppm is added into the second flocculation reaction tank, by water
It supplies film filter (UF film device), carries out film filtration treatment.
In example 6, in addition to by flocculant from polyacrylic polymer (OX-304 (cationic polymer), by
Organo Corporation manufacture) become acrylamide copolymer (AP-1 (anionic polymer)), by Organo
Corporation manufacture) except, film filtration treatment is carried out in a manner of identical with example 5.
In example 7, in addition to by flocculant from polyacrylic polymer (OX-304 (cationic polymer), by
Organo Corporation manufacture) become except polyacrylamide polymer (ON-1H (non-ionic polymers)), by
Organo Corporation manufacture), film filtration treatment is carried out in a manner of identical with example 5.
In example 8, in addition to coagulating agent is become iron chloride (FeCl from PACL3) except, in a manner of identical with example 5
Carry out film filtration treatment.
In example 9, in addition to coagulating agent is become iron chloride (FeCl from PACL3) except, in a manner of identical with example 6
Carry out film filtration treatment.
In example 10, in addition to coagulating agent is become iron chloride (FeCl from PACL3) except, with side identical with example 7
Formula carries out film filtration treatment.
(comparative example 5 to 7)
In comparative example 5, other than not adding coagulating agent, film filtration treatment is carried out in a manner of identical with example 5.
In comparative example 6, other than not adding coagulating agent, film filtration treatment is carried out in a manner of identical with example 6.
In comparative example 7, other than not adding coagulating agent, film filtration treatment is carried out in a manner of identical with example 7.
In example 5 to example 10 and comparative example 5 into comparative example 7, measurement is from water supply start to film filter up to obtaining
Obtain 200ml filtrate the time it takes (filtration time).As the result is shown in table 4.Longer filtration time meaned filtration resistance
Power increase is faster.
[table 4]
Compared with the comparative example 5 to comparative example 7 for wherein only adding flocculant, wherein being added to the reality of flocculant and coagulating agent
Example 5 respectively shows shorter filtration time to example 10.In other words, it may be said that compared with 5 to 7 comparative example of comparative example, in reality
Example 5 preferably inhibits any increase of filtration resistance into example 10.
Reference signs list
1 to 6: processing system
10: the first flocculation reaction tanks
12: flocculant adds pipeline
14: flocculating setting tank
15: coagulator adding set
16: coagulator adds pipeline
18: the second flocculation reaction tanks
20: film filter
22: water pipeline to be processed
24a-24c: connecting pipeline
26,26a, 26b: processing water pipeline
28a, 28b: blender
29: oxidant adding set
30: oxidant adds pipeline
32: activated-carbon device
34: reverse osmosis membrane apparatus
36: penetrating fluid pipeline
38: concentrate pipeline
40:pH regulator adding set
42:pH regulator adds pipeline
44: water quality detecting device
46: control unit
48: bright lattice Lear saturation index calculating section
The amount control section of 50:pH regulator
Claims (11)
1. a kind of membrane filtering method, comprising: coagulating agent is added into processing water, the processing water is by adding into pending water
Enter flocculant and carries out what flocculation and settlement treatment or flocculation were prepared with dissolved air floatation processing；With carry out ultrafiltration membrane treatment and micro-
At least one of filter membrane processing film filtration treatment.
2. membrane filtering method according to claim 1, wherein when carrying out the film filtration treatment, carry out to the place
It manages water to apply shearing force and add at least one of oxidant into the processing water, so that the wadding in the processing water
Molecular cut off of the average molecular weight of solidifying agent no more than film used in the film filtration treatment.
3. membrane filtering method according to claim 1 or 2, wherein the additive amount of the coagulating agent is in the pending water
In 0.5 times to 75 times of concentration (mg/L) of the flocculant in the range of.
4. membrane filtering method according to any one of claim 1 to 3, wherein according to by flocculation and settlement treatment
Or flocculation and dissolved air floatation processing the processing water in by the concentration of the LC-OCD polymerized organics detected to control
State the additive amount of coagulating agent.
5. membrane filtering method according to any one of claim 1 to 4, wherein to the place Jing Guo the film filtration treatment
It manages water and carries out the post-processing of at least one of active carbon processing and reverse osmosis membrane processing.
6. membrane filtering method according to any one of claim 1 to 5, wherein when carrying out the film filtration treatment, control
The pH of the processing water is made, so that the bright lattice Lear saturation index (LSI) of the processing water is less than 0.
7. a kind of membrane filtration system, comprising:
Coagulating agent adding unit, for adding coagulating agent into processing water, the processing water is by being added into pending water
Flocculant simultaneously carries out what flocculation and settlement treatment or flocculation were prepared with dissolved air floatation processing；With
Film filtration treatment unit, the film filtration treatment unit have at least one of ultrafiltration membrane and microfiltration membranes, and to having added
Film filtration treatment is carried out added with the processing water of the coagulating agent.
8. membrane filtration system according to claim 7, further includes:
At least one of shearing force applying unit and oxidant adding unit, the shearing force applying unit are used for the place
It manages water and applies shearing force, the oxidant adding unit is used to add oxidation into the processing water in the film filtration treatment
Agent, wherein
At least one of apply the shearing force and add described oxidant the flocculant ensured in the processing water
Molecular cut off of the average molecular weight no more than film used in the film filtration treatment.
9. membrane filtration system according to claim 7 or 8, wherein the additive amount of the coagulating agent is in the pending water
In 0.5 times to 75 times of concentration (mg/L) of the flocculant in the range of.
10. membrane filtration system according to any one of claims 7 to 9,
With post-processing unit, for being post-processed to the processing water Jing Guo the film filtration treatment, wherein
The post-processing unit is at least one of active carbon processing unit and reverse osmosis membrane processing unit.
11. membrane filtration system according to any one of claims 7 to 10, further includes: pH control unit, the pH control
Unit is used to control the pH of the processing water, so that the bright lattice Lear of the processing water is full when carrying out the film filtration treatment
With index (LSI) less than 0.
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| PCT/JP2017/026324 WO2018030109A1 (en) | 2016-08-08 | 2017-07-20 | Membrane filtration method and membrane filtration system |
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