CN107337259A - A kind of sour wastewater treatment equipment using membrane technology - Google Patents
A kind of sour wastewater treatment equipment using membrane technology Download PDFInfo
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- CN107337259A CN107337259A CN201710538089.0A CN201710538089A CN107337259A CN 107337259 A CN107337259 A CN 107337259A CN 201710538089 A CN201710538089 A CN 201710538089A CN 107337259 A CN107337259 A CN 107337259A
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- 239000012528 membrane Substances 0.000 title claims abstract description 145
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 44
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
- B01D63/043—Hollow fibre modules comprising multiple hollow fibre assemblies with separate tube sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/063—Underpressure, vacuum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of sour wastewater treatment equipment using membrane technology, solves the technical problem that sour waste water treatment process complexity, high energy consumption, integrated cost are high in the prior art.The sour wastewater treatment equipment includes treatment tank, membrane module unit is provided with the treatment tank, pass through the membrane module unit filter acid waste water, the membrane module unit includes bearing shell, more external-compression type membrane tubes are provided with the bearing shell, the bearing shell both ends are respectively arranged with water inlet and delivery port, and the external-compression type membrane tube includes supporting layer, separating layer is provided with outside the supporting layer, the separating layer uses multifunctional graphite vinyl/polymer composite water permeable membrane.The present invention has the features such as structure design is simple, easy to operate, handling process is simple, and energy consumption is low, and integrated cost is low.
Description
Technical field
The present invention relates to a kind of wastewater treatment equipment, and in particular to a kind of sour wastewater treatment equipment using membrane technology, can
For processing hydrochloric acid waste water etc..
Background technology
Development has been paradox the most prominent since entering 21 century with environmental issue, and the water pollution among environmental issue
Again especially prominent, the problem of resolving sewage and waste water, just receives mondial extensive concern.There is external expert film
The development of technology is included among " the third time industrial revolution ", and Germany is then answered using membrane technology as innovating technologies for 21 century
With research and development, and carry forward vigorously applied to field of Environment Protection.Application study especially in water process, with its excellent effluent quality,
Among practical application, the application of the developed country such as U.S., day, West Europe is most.Because membrane technology development cost are high, therefore in development
The popularization paces of country are slow.But, China is had an optimistic view of extensively in terms of membrane technology in recent years.With the gradual increasing of world population
Add, the sanitary sewage daily output has become the global problem for being badly in need of solving.Sanitary sewage because water-quality constituents is by a relatively simple,
Conventional absorbtion, precipitation, biochemical treatment can reach discharge standard.But processing procedure is cumbersome and complicated, the application substitution of membrane technology
Flow relatively excessive materializing strategy program.Technique waste water composition is complicated with respect to sanitary sewage, such as Chemical Manufacture, steel row
Industry, Electroplate Factory etc. can all produce substantial amounts of acid waste water, not only containing acid and water, can also there is substantial amounts of Fe ions or Al ions
It is big Deng metal ion, intractability.General convention acidic sewage firstly the need of carry out plus alkali in and forming salt, then pass through roasting
Handled etc. technique, this complex technical process and cost is too high.The application of membrane technology is with its excellent producing water water quality, in production water
It is required that it is high, have more deep processing requirement, concentration of wastewater high or the limited water treatment field such as Sewage treatment requirement obtains especially
It is widely applied.
Waste sewage, which handles common process, at present mainly ion-exchange-resin process, sudden to follow the example of, roasting method, neutralizes
Oxidizing process, and concentration method.
1. ion-exchange-resin process.Document《The regeneration of waste hydrochloric acid》Middle report has using certain absorbs HCl functions
Ion exchange resin can realize separation hydrochloric acid purpose.But the concentration of hydrochloric acid that this method reclaims at normal temperatures is extremely low, and needs
Adding a large amount of supplementary elements could use, and can not realize a large amount of industrial treatments.
2. sudden follow the example of.This method mixes principle to separate spent acid using similar, but this method has secondary pollution, and separates
Not exclusively.
3. roasting method.This method is that after waste hydrochloric acid containing iron sewage is atomized, hydrogen chloride gas is thermally decomposed into roaster
And frerrous chloride, wherein hydrogen chloride gas are discharged from furnace roof and reclaim collection, frerrous chloride is oxidized to iron chloride and falls into furnace bottom.
This method high energy consumption, recovery system are complicated.
In 4. and oxidizing process.Among some steel industries of China, to waste hydrochloric acid, most of the processing of Waste Sulfuric Acid is all to use
The method of acid-base neutralization, reprocessing salt after making pH value up to standard.But this method process treatment process is complicated, the salt recovery difficult of generation
Greatly, the problems such as cost is high, and treatment effect is barely satisfactory limits extensive use.
5. concentration method.It is to obtain the method for concentrate by the aqueous water among waste sewage is evaporated, the operation letter of this method
It is single, but the energy consumption problem that brings of high temperature evaporation is always the problem that numerous enterprises are difficult to overcome.Concentration method is acknowledged as always
The most thoroughly also never stopped with efficient method, the research and development of various concentration techniques among all spent acid handling process.
In recent years, the research and development of new membrane technology concentrated acidic waste water have obtained more in-depth study, and it is based on film point
From the water process new technology of material.Research starts from the U.S. of the 1960s, by the pioneering research and development of Dorr-Oliver companies.With
The continuous development of technology, various new membrane materials also constantly come out.Divide because the technology passes through the efficient of membrane module
From effect, there is the trend for gradually substituting traditional water process.In summary the characteristics of membrane technology treatment technology：
1. the membrane aperture of membrane technology is controlled below≤0.4 μm, solid- liquid separation, producing water water quality mark can be effectively carried out
Accurate high, stay in grade, micro- float and turbidity are low, can suitably select reuse according to industrial application standard.
2. membrane technology has effect of efficiently damming, microorganism can be made to dam completely in reactor, reactor water can be achieved
Power residence time (HRT) and sludge age (SRT's) is kept completely separate so that system operation controls more long-acting stabilization.
3. membrane technology is advantageous to breed the damming of slow nitrobacteria and other bacteriums, growth and breeding, at overall sewage
The index such as reason system nitrification efficiency and reduction COD value is improved.
4. the modularized design of membrane technology can effective utilization space, volumetric loading is high, takes up an area few, and Operation and Maintenance is simple
It is convenient and swift, equally it is also convenient for dilatation.Meanwhile controlled using PLC, automatic control management can be achieved.
In summary, the technique of membrane technology processing waste water, has the characteristics of conventional processing technique is incomparable.At present, by
In the acid system and ionic species of sour water, such sewage, water filtration membrane often can not be handled with membrane material using in the market
Material can not adapt to extremely harsh processing environment, and the problems such as salt component can not be separated.Membrane aperture is controlled at 0.1 μm -0.4 mostly
Between μm, ion or microorganism less than 0.1 μm can equally pass through membrane material, influence effluent quality.And long-term disposal is such
Sewage, common drainage membrane material are influenceed by indomitable microorganism unavoidably, and Kong Yi is blocked by fine particle or bacterial micro-organism, or film
Surface breed bacteria influences water flux.As the production water after the processing of domestic number of patent application 200410012228.9 need to be sent into ozone pond
Middle progress sterilization processing could be discharged or technique uses again.And for example Chinese Patent Application No. 201110269978.4 uses
The segregated sewage salinity of dewatering microporous film, the larger limitation of acid-base value.
The content of the invention
For the above-mentioned problems in the prior art, the invention provides a kind of sour wastewater treatment dress using membrane technology
Put, be provided with membrane module unit, by membrane module unit filter acid waste water, sour waste water is after filtering in membrane module unit
Portion forms vapor, then to being discharged after vapor cooling liquid, so as to reach industrial treatment, simplify handling process, reduce into
This purpose of, it can be used for handling various sour waste water.
In order to achieve the above object, the technical proposal of the invention is realized in this way：
The present invention provides a kind of sour wastewater treatment equipment using membrane technology, including treatment tank, the sewage disposal
Membrane module unit is provided with pond, by the membrane module unit filter acid waste water, sour waste water is after filtering in the membrane module
Unit is internally formed vapor, and the delivery port of the membrane module unit is connected to heat exchanger by pipeline, and the heat exchanger passes through
Pipeline connects condensing unit, and the vapor being filtrated to get is inputted to heat exchanger, in the heat exchanger from the membrane module unit
In be cooled liquefaction after discharge, the heat exchanger is connected to aqua storage tank by pipeline.
Further, the sour waste water in the treatment tank is in and circulates state, the axial direction of the membrane module unit
It is be arranged in parallel with the flow direction of the sour waste water；Sour waste water circulation flow velocity in the treatment tank is 40-80cm/s, institute
It is 50-70 DEG C to state the sour wastewater temperature in treatment tank.
Further, the sour waste water circulation flow velocity in the treatment tank is 60cm/s, the acid in the treatment tank
Wastewater temperature is 55 DEG C.
Further, the aqua storage tank by pipeline connect negative pressure system, the negative pressure system can provide -0.093MPa to -
Negative pressure between 0.098MPa, it is negative that the negative pressure system make it that the membrane module unit, heat exchanger and aqua storage tank are internally formed
Pressure.
Further, in the condensing unit coolant temperature≤20 DEG C；In the heat exchanger, in negative pressure -0.093MPa
When following, dew point≤20 DEG C of saturated steam.
Further, the pipe joint of the negative pressure system connection aqua storage tank is located at the aqua storage tank top, described negative
Pressure system, which connects, is provided with molecular filtration sieve in the pipeline of the aqua storage tank, prevent hydrone from entering in the negative pressure system.
Further, upper and lower two controlled valves are provided with the aqua storage tank, are water storage between upper and lower two controlled valves
Chamber, the upper switch valve are located at the position below negative port；Upper switch valve is closed in draining, opens lower switch valve
Door, lower switch valve is closed in water storage, open upper switch valve.
Further, the negative pressure system can provide the negative pressure between -0.095MPa to -0.098MPa, the condensing unit
The temperature of middle coolant is -5 DEG C to 18 DEG C.
Further, the treatment tank is provided with water circulating pipe, and the water circulating pipe has water inlet and water outlet
Mouthful；Having heaters is set in the treatment tank to sour waste water heat temperature raising；The water inlet of the water circulating pipe is arranged on
It is arranged on close to the position of the treatment tank bottom, and away from the heater, the delivery port of the water circulating pipe
Position at the top of the treatment tank, and close to the heater.
Further, heat exchanger fin is provided with the heat exchanger, the heat exchanger fin surface is coated with equadag coating；The heating
Spiral shape heater strip is provided with device.
Further, filter mantle is installed outside the membrane module unit, multiple honeycomb holes are provided with the filter mantle, or
Filter mantle described in person is grid-like.
Further, the membrane module unit includes bearing shell, and more external-compression type membrane tubes are provided with the bearing shell,
The bearing shell both ends are respectively arranged with water inlet and delivery port, and the external-compression type membrane tube includes supporting layer, the supporting layer
Outside is provided with separating layer, and the separating layer uses multifunctional graphite vinyl/polymer composite water permeable membrane.
Further, the separating layer is to equal the encapsulated by structures of volume or helical coil on the supporting layer, in seam crossing with ring
Oxygen tree fat or polyurethane adhesive, or thermal compression welding.
Further, the bearing shell includes circular cylinder body, and the circular cylinder body both ends are respectively arranged with upper end cover with
End cap, the water inlet are arranged on the bottom end cover, and the delivery port is arranged on the upper end cover.
Further, the inside that is axially disposed within the circular cylinder body of the external-compression type membrane tube along the circular cylinder body, institute
State the both ends that external-compression type membrane tube both ends are glued respectively to the circular cylinder body.
Further, concentrated solution outlet is additionally provided with the upper end cover, reserved opening is provided with the circular cylinder body.
Further, the supporting layer material is PE, PES, PVDF, PVC, PP or ceramics；The material of the bearing shell is
PVC, PP or ABS.
Further, aperture≤0.1nm of the multifunctional graphite vinyl/polymer composite water permeable membrane.
Further, the supporting layer uses seven core hollow fiber conduits of PES materials, and the tube wall of the hollow fiber conduit is micro-
Pore structure, aperture 0.1-0.3nm；The external-compression type membrane tube external diameter is 3.8mm.
Further, the pressure that the separating layer is born is not less than 0.5MPa, and thermal conductivity factor is not less than 0.5W/mK, heat-resisting temperature
Spend for 200 DEG C.
The sour wastewater treatment equipment set using said structure has advantages below：
1. effluent quality high-quality stable.Graphene/nanometer polymeric membrane technology of the present invention has efficient point
From effect, separating effect is significantly larger than the sewage disposal systems such as traditional sedimentation basin.Molecule among sewage is substantially complete
Dam out entirely, ensure that water outlet is as clear as crystal, suspension and turbidity are essentially close to zero.And due to film skill of the present invention
The characteristics of art aperture is less than 0.1nm, and its membrane technology only allows hydrone to pass through membrane material make it that effluent quality is very high.Its water outlet water
Life impurity of fine quality in Ministry of Construction water water standard (CJ25.1-89), it can be directly used for non-municipal usage of drinking and carry out
Recovery.
2. membrane module service life is grown.Because the graphene/nanometer polymeric membrane that this programme uses also has antibiotic and sterilizing
Effect, therefore bacterium and virus can be removed largely, largely reduce membrane material by the possibility of biological damage, greatly
The big ability for improving membrane module processing sewage, increases the service life.
3. membrane module is without backwash.Currently used business membrane module is required to be backwashed, such as MBR, RO films etc.
It is unfinished to reach good filter effect, backwash process must be carried out after short time use.This process not only reduces water process
Efficiency, and system architecture unit must increase backwash parts, increase extra cost burden.Processing disclosed by the invention
Device, without carrying out backwash process, substantially increase water treatment efficiency and reduce processing cost.
4. membrane module has wide range of applications, can be used for handling sulfuric acid waste, hydrochloride waste, phosphate discharge liquid, acetic acid waste liquid
Deng acid waste liquid.Graphene/nanometer polymeric membrane component of the present invention is hollow fiber form structure, can be directly immersed in dirt
Among water, because sewage is in continuous flow regime, molecule is not easy in film surface sediment.And due to graphene/nanometer height
The particularity of molecule membrane material, membrane module can only need surface washing etc. in pH value of sewage water in 0-14 normal works after long-term work
Simple cleaning, without changing component.
5. a kind of sour wastewater treatment equipment using membrane technology provided by the invention, simple with structure design, easy to operate,
The features such as handling process is simple, and energy consumption is low, and integrated cost is low.
6. graphene/polymer membrane material of the present invention is to rejection >=99% of metal ion.Membrane aperture exists
Below 0.1nm, hole plug problem is substantially not present, meanwhile, aqueous water is by membrane material, so production water water in the form of hydrone
Matter is greatly improved.
Brief description of the drawings
Fig. 1 is the structural representation of the sour wastewater treatment equipment of the present invention；
Fig. 2 is the structural representation of the sour wastewater treatment equipment of the present invention；
Fig. 3 is the liquid path schematic diagram of the sour wastewater treatment equipment of the present invention；
Fig. 4 is the structural representation that the present invention uses tubular membrane component；
Fig. 5 is along A-A sectional view in Fig. 4；
Fig. 6 is the fixed structure schematic diagram that tubular membrane component uses external-compression type membrane tube in bearing shell；
Fig. 7 is the structural representation that tubular membrane component uses external-compression type membrane tube in embodiment 1；
Fig. 8 is the structural representation that tubular membrane component uses external-compression type membrane tube in embodiment 2；
Fig. 9 is along B-B sectional view in Fig. 7, Fig. 8；
Figure 10 is the profile of separating layer in external-compression type membrane tube.
In figure：11. membrane module unit；11-1. membrane tubes；11-2. separating layers；11-3. supporting layers；11-4. modified graphene/
Nanostructured multifunctional macromolecule material；11-5. microcellular polymeric material basement membrane；11-6. bearing shells；11-7. upper end covers；
11-8. bottom end covers；11-9. water inlets；11-10. delivery ports；11-11. concentrated solution outlets；11-12. reserved openings；11-13. embeddings
Glue；
12. heat exchanger；13. condensing unit；14. negative pressure system；15. heater；16. treatment tank；17. water-circulating pump
Body；
21. aqua storage tank；22. condensed water outlet conduit；23. condensed water inlet channel；24. clear water transport pipeline；It is 25. external
Water circulating pipe；26. circuit switch board.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail.
Embodiment 1
It is the embodiment of the present invention 1, in this embodiment, a kind of sour waste water using membrane technology as shown in Figure 1, Figure 2, Figure 3 shows
Processing unit, including treatment tank 16, membrane module unit 11 is provided with treatment tank 16, passes through the mistake of membrane module unit 11
Acid filtering waste water.Membrane module unit 11 includes bearing shell 11-6, and more external-compression type membrane tube 11-1 are provided with bearing shell 11-6,
Bearing shell 11-6 both ends are respectively arranged with water inlet 11-9 and delivery port 11-10.
As shown in Figure 4, Figure 5, external-compression type membrane tube 11-1 includes supporting layer 11-3, and separating layer is provided with outside supporting layer 11-3
11-2, separating layer 11-2 use multifunctional graphite vinyl/polymer composite water permeable membrane.Used multifunctional graphite vinyl/height
Aperture≤0.1nm of molecular composite material water permeable membrane.
Sour waste water in treatment tank 16 is in and circulates state, is so to allow concentration, the temperature of sour waste water
Uniform state is in etc. parameter.External-compression type membrane tube 11-1 axial direction and the flow direction of sour waste water be arranged in parallel, is advantageous to flow
Hydrodynamic body takes away the impurity on film surface.
Sour waste water circulation flow velocity in treatment tank 16 is 40-80cm/s, is preferably during for handling hydrochloric acid waste water
60cm/s.Sour wastewater temperature in treatment tank 16 is 50-70 DEG C, is preferably 55 DEG C during for handling hydrochloric acid waste water.
Sour waste water is internally formed vapor, the delivery port 11- of membrane module unit 11 in external-compression type membrane tube 11-1 after filtering
10 are connected to heat exchanger 12 by clear water transport pipeline 24, and heat exchanger 12 passes through condensed water outlet conduit 22 and condensed water water inlet pipe
Road 23 connects condensing unit 13, and the vapor being filtrated to get is inputted to heat exchanger 12 from external-compression type membrane tube 11-1, in heat exchanger
It is cooled after liquefying and discharges in 12.
Heat exchanger 12 connects aqua storage tank 21 by pipeline, and aqua storage tank 21 connects negative pressure system 14, negative pressure system by pipeline
14 can provide the negative pressure between -0.093MPa to -0.098MPa, be preferably -0.095MPa to -0.098MPa.Negative pressure system 14
So that external-compression type membrane tube 11-1, heat exchanger 12 and aqua storage tank 21 are internally formed negative pressure.
Temperature≤20 DEG C of coolant in condensing unit 13, it is preferably -5 DEG C to 18 DEG C；In heat exchanger 12, negative pressure-
Dew point≤20 DEG C of saturated steam, it is preferably -5 DEG C to 18 DEG C during below 0.093MPa.
The pipe joint that negative pressure system 14 connects aqua storage tank 21 is located at the top of aqua storage tank 21.Condensed aqueous water is in gravity
Excluded under effect from aqua storage tank 21, the interface of negative pressure system 14 is arranged on effluent trough vertically upward, is pushed up positioned at aqua storage tank 21
End position, being advantageous to aqueous water will not pour in down a chimney among negative pressure system 14.
Negative pressure system 14, which connects, is provided with molecular filtration sieve in the pipeline of aqua storage tank 21, prevent hydrone from entering negative pressure system
In 14.
Upper and lower two controlled valves are provided with aqua storage tank 21, are water storage cavity between upper and lower two controlled valves, upper switch
Valve is located at aqua storage tank 21 and connects position below the negative port of negative pressure system 14, can so allow negative pressure from aqua storage tank 21 1
Direct transfer and be handed to heat exchanger 12；Upper switch valve is closed in draining, opens lower switch valve, lower switch valve is closed in water storage
Door, open upper switch valve.It in order to ensure in system is low-pressure state that so design, which is, is maintained below -0.093MPa.
Treatment tank 16 is provided with external water circulating pipe 25, and the water circulation pump housing is provided with external water circulating pipe 25
17。
External water circulating pipe 25 has water inlet and delivery port；Set having heaters 15 useless to acid in treatment tank 16
Water heat temperature raising；The water inlet of external water circulating pipe 25 is positioned close to the position of the bottom for the treatment of tank 16, and remote
Heater 15, the delivery port of external water circulating pipe 25 are positioned close to the position at the top for the treatment of tank 16, and close to plus
Hot device 15.
Heat exchanger fin is provided with heat exchanger 12, heat exchanger fin surface is coated with equadag coating, can reduce minimal amount of in production water
HCL exchanges the corrosion of backing, causes the secondary pollution problems such as producing water water quality decline.
Spiral shape heater strip is provided with heater 15.The temperature eat source of raw water is not restricted to additional auxiliary heating, such as
Fruit source of sewage has certain temperature in itself, while disclosure satisfy that the temperature conditionss of technique, also sewage directly can be carried out into concentration point
From processing.
Filter mantle is installed outside membrane module unit 11, multiple honeycomb holes are provided with filter mantle, or filter mantle is lattice
Palisade.Filter mantle can play a part of completely cutting off large scale debris.
As Fig. 4, Fig. 5, Fig. 6, Fig. 7 show the concrete structure of membrane module unit 11, including bearing shell 11-6, outside pressure-bearing
More external-compression type membrane tube 11-1, bearing shell 11-6 both ends are provided with shell 11-6 and are respectively arranged with water inlet 11-9 and delivery port
11-10。
As shown in Figure 7, Figure 8, external-compression type membrane tube 11-1 includes supporting layer 11-3, and separating layer is provided with outside supporting layer 11-3
11-2, separating layer 11-2 use multifunctional graphite vinyl/polymer composite water permeable membrane.
Multifunctional graphite vinyl/polymer composite water permeable membrane is product of the prior art, in Chinese invention patent
Institute in CN2015105675811 " a kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use "
It is open.
Multifunctional graphite vinyl/polymer composite water permeable membrane, as shown in Figure 10, using modified graphene/nanostructured
Multifunctional macromolecule material 11-4 is compounded on microcellular polymeric material basement membrane 11-5 and is made.
The modified graphene that wherein uses and wet high molecular polymer is led with height, pass through the polar group in molecular structure
Group forms the chemical bond linkages such as hydrogen bond, covalent bond, has extremely strong corrosion resistance and resistance to acids and bases, and extraordinary antibacterial is killed
Bacterium property.
The water-wet side absorption aqueous water on multifunctional graphite vinyl/polymer composite water permeable membrane surface, membrane material both sides are shape
Into water vapor concentration gradient difference, under negative pressure (inside external-compression type membrane tube 11-1) synergy, aqueous water is gradually with hydrone
Form pass through membrane material.
Microcellular polymeric material basement membrane 11-5 materials are PAN, PE, PS, PES, PVDF, PVC, PT, PSU, PTFE or PP.It is excellent
Choosing uses PE.
As shown in fig. 7, separating layer 11-2, to equal the encapsulated by structures of volume on supporting layer 11-3, separating layer 11-2 is one whole
, one layer of volume is put down, in seam crossing with epoxy resin or polyurethane adhesive, or thermal compression welding so that separating layer 11-2 and support
Layer 11-3 is closely joined together.
As shown in Figure 4, Figure 5, bearing shell 11-6 includes circular cylinder body, and circular cylinder body both ends are respectively arranged with upper end cover
11-7 and bottom end cover 11-8, water inlet 11-9 are arranged on bottom end cover 11-8, and delivery port 11-10 is arranged on upper end cover 11-7.
Bearing shell 11-6 material can select PVC, PP or ABS etc..
Delivery port 11-10 connection negative pressure equipment (not shown)s, the interior outsides of external-compression type membrane tube 11-1 have pressure difference, moisture
Son on the outside of external-compression type membrane tube 11-1 by entering on the inside of external-compression type membrane tube 11-1.
The inside that is axially disposed within circular cylinder body of the external-compression type membrane tube 11-1 along circular cylinder body, external-compression type membrane tube 11-1 both ends
It is glued respectively to the both ends of circular cylinder body.As shown in fig. 6, external-compression type membrane tube 11-1 upper ends are fixed with casting glue 11-13, external-compression type
Membrane tube 11-1 is also fixed (not shown in Fig. 6) lower end with casting glue 11-13.
Because the clear water being filtrated to get exports inside external-compression type membrane tube 11-1, acid waste liquid needs to enter external-compression type membrane tube
Outside 11-1, so external-compression type membrane tube 11-1 upper end outlets need to stretch out from the casting glue 11-13 of upper end, external-compression type membrane tube 11-1
Lower inlet needs, by the casting glue 11-13 closings of lower end, to correspond to lower end water inlet 11-9 the casting glue 11-, it is necessary in lower end
Intake tunnel is set to be input to by acid waste liquid inside bearing shell 11-6 on 13.
As shown in figure 4, being additionally provided with concentrated solution outlet 11-11 on upper end cover 11-7, reserved opening is provided with circular cylinder body
11-12。
Concentration acid waste liquid after concentrated solution outlet 11-11 discharge filterings.Reserved opening 11-12 is to close during component normal operation
, it can enable reserved opening 11-12 when component occurs abnormal.
Supporting layer 11-3 materials are PE, PES, PVDF, PVC, PP or ceramics.Supporting layer 11-3 during for handling hydrochloric acid waste water
It is preferred that the seven core hollow fiber conduits using PES materials.
As shown in figure 9, seven cored structure reinforcing fibre pipe support strengths, the tube wall of hollow fiber conduit are used in hollow fiber conduit
For microcellular structure, aperture 0.1-0.3nm.
As shown in figure 9, external-compression type membrane tube 11-1 outside diameter d is 3.8mm.
The pressure that separating layer 11-2 is born is not less than 0.5MPa, and thermal conductivity factor is not less than 0.5W/mK, heat resisting temperature 200
℃。
It is 3.354 × 10 from a kind of electrical conductivity5μ s/cm, solid content are 20-21% (mass fraction), and sulfuric acid content is
The Acidic water of 15% (mass fraction) is tested the tubular membrane component in the present invention.External-compression type membrane tube 11-1 internal diameters
25mm, external diameter 34mm, effective membrane area 0.025m2, waste water by pretreatment, removes more than 25 μm granule foreign things, former
Water pH value is less than 1.Producing water water quality is analyzed, production water conductivity is 6 μ s/cm, and permeant flux is 12.32kg/ (m2H),
It is 6.5 to produce water ph value.
A kind of external-compression type tubular membrane component for wastewater treatment of the invention when in use, removes suspension by pretreatment
Acid pickle after water inlet 11-9 entrance, concentrated by external-compression type membrane tube 11-1 purifying, can obtain high-quality production water and dense
Contracting acid solution.Production water can directly discharge or it is secondary be used for industrial production, highly concentrated acid solution can centralized recovery, greatly reduce useless
The cost of sulfuric acid treating processes, and can also be in high efficiente callback waste liquid sulfuric acid, produce enormous industrial benefit.
Embodiment 2
In this embodiment, with embodiment 1 except that, as shown in figure 8, separating layer 11-2 is with the structure bag of helical coil
Be rolled on supporting layer 11-3, in seam crossing with epoxy resin or polyurethane adhesive, or thermal compression welding so that separating layer 11-2 with
Supporting layer 11-3 is closely joined together.
Fig. 8 is only structural representation, in separating layer 11-2 winding process each circle separating layer 11-2 be required for up and down
The close linking transition of circle.
The structure of helical coil, the separating layer 11-2 parcel supporting layers 11-3 of narrower width can be used.
The other structures of tubular membrane component are same as Example 1 in the present embodiment, are not repeated to describe herein.
The present invention also provides a kind of using upper in addition to providing sour wastewater treatment equipment of the one of the above using membrane technology
The sewage water treatment method that sour wastewater treatment equipment is carried out is stated, specific method step is as follows：
(1) sewage in cesspool is heated by heater, while opens the external water circulation pump housing of cesspool, make sewage
Accessing pending water in pond is among the process constantly circulated；Graphene/nanometer polymeric membrane component direction and current side straight
To being placed in parallel, be advantageous to flow the impurity that aqueous water takes away film surface；
(2) condensing unit is opened, after coolant-temperature gage to be condensed reaches setting value, closes the end valve of aqua storage tank, in opening
End valve door, and open negative pressure system and proceed by sewage disposal.Aqueous water in sewage in the form of hydrone through graphene/
Nano-high molecule film reaches component internal, is transferred under the synergy of negative pressure in heat exchanger, hydrone is condensed into aqueous water
Afterwards again Action of Gravity Field downstream among effluent trough；
(3) after the water among aqua storage tank is certain, aqua storage tank upper end valve is closed, bottom valve goalkeeper aqua storage tank is opened and works as
In water discharge.End valve is closed after emptying production water, slowly opens upper end valve, now the negative pressure of vacuum inside closed system
It can reduce, after negative pressure magnetic valve arranges value is reached, vavuum pump can work automatically to be kept setting pressure, and this process does not interfere with out
Water water quality.
Wherein, treatment sewage described in step (1), should try one's best and be pre-processed, except big of observability among decontaminated water
Grain impurity and organic matter, the membrane technology of the present invention is played a role, improve water treatment efficiency.
Wherein, the temperature of the heating of heater described in step (1) sewage is preferably between 50 DEG C to 70 DEG C；Described is external
The water circulation pump housing, more preferably preferable flow rate 40-80cm/s, 60cm/s.
Wherein, condensate temperature described in step (2) sets preferably≤20 DEG C, more preferably -5 DEG C -18 DEG C.
Experimental example 1
Concentrating and separating processing is carried out from a kind of electrical conductivity (abbreviation EC values) about 120ms/cm waste hydrochloric acid containing iron water.It is described
Waste water by pretreatment, removes 25 μm of (micron) above granule foreign things and part organic principle；Sewage chloride ion content
For 1.51 × 104Mg/L, raw water pH value are less than 1, and iron ion content is 2.14 × 103mg/L。
In order to study influence of the different sewage treatment temperature to effluent quality, the sewage temperature for the treatment of tank 16 is distinguished
It is arranged on 50 DEG C, 60 DEG C and 70 DEG C and has done membrane module sewage concentration separating experiment.The parameter of sour wastewater treatment equipment other parts
Keep identical, i.e., the condensate temperature of condensing unit 13 sets 18 DEG C, and the vacuum of negative pressure system 14 is maintained at -0.095MPa
To -0.098MPa.
The internal heater 15 for the treatment of tank 16 is opened, sewage temperature is arranged on 50 DEG C, at the same processing pond is external
The water circulation pump housing 17 is in running order, and the condensation temperature of condensing unit 13 is arranged to 18 DEG C and carries out condensate water circulatory work.
When arrange parameter reaches stable state, open negative pressure system 14, make its vacuum be maintained at -0.095MPa to -
Between 0.098MPa.
After waste hydrochloric acid containing iron water is handled by apparatus of the present invention, under the conditions of raw water temperature is 50 DEG C, production water is limpid bright.
By analyzing producing water water quality, EC values as little as 30-40us/cm, the chloride ion content 4-6mg/L of water are produced, produces water pH value
Substantially close to neutrality, iron ion content is almost nil.Discharge water standard is fully achieved in producing water water quality, or even production water can be used for
Industrial seconary water use.
Among this experimental example, using raw water water temperature as variable, change water temperature and tested to 60 DEG C.As described above,
Other specification is consistent, i.e. condensate temperature is arranged to 18 DEG C, the vacuum of negative pressure system 14 be maintained at -0.095MPa to -
0.098MPa.After temperature is increased to 60 DEG C, by analyzing producing water water quality, the TDS values of water are produced about to 40-50us/cm,
Chloride ion content is 4-6mg/L, and production water pH value is substantially close to neutrality, iron ion content≤0.2mg/L.
When raw water water temperature is increased to 70 DEG C, by analyzing producing water water quality, the TDS values of water are produced about to 130-
240us/cm, chloride ion content 15-20mg/L, production water pH value is close to 4, iron ion content 0.4-1mg/L.By consulting hydrochloric acid
Boiling characteristics, find the rise with temperature, and the raising of raw water concentrating degree, the volatility of hydrochloric acid is stronger among sewage,
So that HCl gases caused by volatilization penetrate membrane material with water vapour caused by evaporation, so as to be brought among condensed water, so as to make
PH into condensed water is reduced.As the rise of temperature causes producing water water quality slant acidity, while acid water heat exchanging device can also play
Corrosiveness, it is final to cause production water EC value rises.
Experimental example 2
Concentrating and separating processing is carried out from the hydrochloric acid waste water of different EC values, raw water by pretreatment, removes 25 μm
(micron) above granule foreign thing and part organic principle.Producing water water quality is analyzed, data result is as shown in the table, table 1
The water-quality ratio of to be raw water produce later with concentrating and separating water compared with：
The raw water of table 1 and the water quality of production water
A kind of sour wastewater treatment equipment using membrane technology that the present invention utilizes, sour water as described above is carried out dense
Contracting processing has good effect, and cycles of concentration is up to more than 15 times.With the further raising of raw water concentrating degree, or sewage
The raising of temperature, HCl volatility enhancing in condensed water cause to produce that water pH is reduced and EC values raise.The processing unit of the present invention,
Since equipment longtime running six months, producing water water quality is stable.
A kind of sour wastewater treatment equipment using membrane technology of the present invention, it is water that its sewage concentration process, which briefly describes,
The transfer process of molecule, the hydrone in waste water, which is extracted, concentrates raw water, and producing water water quality because indices it is reachable
Discharged to non-municipal usage standard of drinking, or be reused for industrial water, the FeCl in condensed water2At can be by crystallization
Reason separates additive for industrial production or garbage disposal, it is highly concentrated after hydrochloric acid can be used for secondary industrial utilization or
Other use.
Term " dissolvability solid amount " (English in the present invention：Total dissolved solids, abridge TDS),
Show that, dissolved with how many milligrams of soluble solids in 1 liter of water, units of measurement is mg/litre (mg/L).TDS values are higher, represent in water
The dissolved matter contained is more.Total dissolved solidss refer to the total amount of whole solutes in water, include the content of both inorganic matter and organic matter.
A kind of sour wastewater treatment equipment using membrane technology of the present invention, its shape can be designed to cuboid,
Cube or other irregular shapes, wherein membrane module unit may be designed to doughnut tubular type, board-like, or winding type etc., can
Cosmetic variation is carried out according to actual use demand.
In summary, the present invention is a kind of sour wastewater treatment equipment using membrane technology, and using the processing unit
Sewage water treatment method, can be applied to the ions of Fe containing metal concentrated hydrochloric acid sewage disposal industry among, can also be applied to
The sewage disposal of other industry such as metallurgy industry, such as the wastewater treatment of pharmaceuticals industry, and for example wastewater treatment of chemical industry etc..By
Producing water water quality after processing disclosure satisfy that the life impurity water water standard of the Ministry of Construction, directly can be discharged or be used in outdoor
Recycled in non-municipal usage of drinking, great economic benefit can be brought to enterprise, while also mitigate pressure to environment
Power, benefit the nation and the people.
The embodiment of the present invention is these are only, under the above-mentioned teaching of the present invention, those skilled in the art can be with
Other improvement or deformation are carried out on the basis of above-described embodiment.It will be understood by those skilled in the art that above-mentioned specifically retouches
State and simply preferably explain the purpose of the present invention, protection scope of the present invention should be defined by scope of the claims.
Claims (20)
1. a kind of sour wastewater treatment equipment using membrane technology, including treatment tank, film is provided with the treatment tank
Assembly unit, pass through the membrane module unit filter acid waste water, it is characterised in that sour waste water is after filtering in the membrane module list
Member is internally formed vapor, and the delivery port of the membrane module unit is connected to heat exchanger by pipeline, and the heat exchanger passes through pipe
Road connects condensing unit, and the vapor being filtrated to get is inputted to heat exchanger, in the heat exchanger from the membrane module unit
Discharged after cooled liquefaction, the heat exchanger is connected to aqua storage tank by pipeline.
2. sour wastewater treatment equipment as claimed in claim 1, it is characterised in that the sour waste water in the treatment tank is in
State is circulated, the axial direction of the membrane module unit and the flow direction of the sour waste water be arranged in parallel；The sewage disposal
Sour waste water circulation flow velocity in pond is 40-80cm/s, and the sour wastewater temperature in the treatment tank is 50-70 DEG C.
3. sour wastewater treatment equipment as claimed in claim 2, it is characterised in that the sour waste water circulation in the treatment tank
Flow velocity is 60cm/s, and the sour wastewater temperature in the treatment tank is 55 DEG C.
4. sour wastewater treatment equipment as claimed in claim 1, it is characterised in that the aqua storage tank connects negative pressure system by pipeline
System, the negative pressure system can provide the negative pressure between -0.093MPa to -0.098MPa, and the negative pressure system causes the film group
Part unit, heat exchanger and aqua storage tank are internally formed negative pressure.
5. sour wastewater treatment equipment as claimed in claim 4, it is characterised in that the temperature of coolant in the condensing unit≤
20℃；In the heat exchanger, when below negative pressure -0.093MPa, dew point≤20 DEG C of saturated steam.
6. sour wastewater treatment equipment as claimed in claim 4, it is characterised in that the negative pressure system connects the aqua storage tank
Pipe joint is located at the aqua storage tank top, and the negative pressure system connects in the pipeline of the aqua storage tank and is provided with molecular filtration
Sieve, hydrone is prevented to enter in the negative pressure system.
7. sour wastewater treatment equipment as claimed in claim 4, it is characterised in that upper and lower two are provided with the aqua storage tank
Controlled valve, it is water storage cavity between upper and lower two controlled valves, the upper switch valve is located at the position below negative port；
Upper switch valve is closed during draining, opens lower switch valve, lower switch valve is closed in water storage, opens upper switch valve.
8. sour wastewater treatment equipment as claimed in claim 5, it is characterised in that the negative pressure system can provide -0.095MPa
To the negative pressure between -0.098MPa, the temperature of coolant is -5 DEG C to 18 DEG C in the condensing unit.
9. sour wastewater treatment equipment as claimed in claim 1, it is characterised in that the treatment tank is provided with water-circulating pipe
Road, the water circulating pipe have water inlet and delivery port；Having heaters is set to heat sour waste water in the treatment tank
Heating；The water inlet of the water circulating pipe is positioned close to the position of the treatment tank bottom, and adds away from described
Hot device, the delivery port of the water circulating pipe is positioned close to the position at the top of the treatment tank, and adds close to described
Hot device.
10. sour wastewater treatment equipment as claimed in claim 9, it is characterised in that heat exchanger fin, institute are provided with the heat exchanger
State heat exchanger fin surface and be coated with equadag coating；Spiral shape heater strip is provided with the heater.
11. sour wastewater treatment equipment as claimed in claim 1, it is characterised in that be provided with outside the membrane module unit
Filter bowl, multiple honeycomb holes, or the filter mantle are provided with the filter mantle to be grid-like.
12. sour wastewater treatment equipment as claimed in claim 1, it is characterised in that the membrane module unit includes bearing shell,
More external-compression type membrane tubes are provided with the bearing shell, the bearing shell both ends are respectively arranged with water inlet and delivery port,
The external-compression type membrane tube includes supporting layer, and separating layer is provided with outside the supporting layer, and the separating layer uses multi-functional graphite
Alkene/polymer composite water permeable membrane.
13. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the separating layer is with flat volume or helical coil
Encapsulated by structures is on the supporting layer, in seam crossing with epoxy resin or polyurethane adhesive, or thermal compression welding.
14. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the bearing shell includes circular cylinder body,
The circular cylinder body both ends are respectively arranged with upper end cover and bottom end cover, and the water inlet is arranged on the bottom end cover, it is described go out
The mouth of a river is arranged on the upper end cover.
15. sour wastewater treatment equipment as claimed in claim 14, it is characterised in that the external-compression type membrane tube is along the circular cylinder
The inside for being axially disposed within the circular cylinder body of body, the external-compression type membrane tube both ends are glued respectively to the two of the circular cylinder body
End.
16. sour wastewater treatment equipment as claimed in claim 14, it is characterised in that be additionally provided with concentrate on the upper end cover
Export, reserved opening is provided with the circular cylinder body.
17. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the supporting layer material be PE, PES,
PVDF, PVC, PP or ceramics；The material of the bearing shell is PVC, PP or ABS.
18. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the multifunctional graphite vinyl/macromolecule is multiple
Aperture≤0.1nm of condensation material water permeable membrane.
19. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the supporting layer uses the seven of PES materials
Core hollow fiber conduit, the tube wall of the hollow fiber conduit are microcellular structure, aperture 0.1-0.3nm；Outside the external-compression type membrane tube
Footpath is 3.8mm.
20. sour wastewater treatment equipment as claimed in claim 12, it is characterised in that the pressure that the separating layer is born is not less than
0.5MPa, thermal conductivity factor are not less than 0.5W/mK, and heat resisting temperature is 200 DEG C.
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