CN107096393A - A kind of thermally-stabilised, super-hydrophobic ceramic carbon nano-tube compound film and its membrane distillation water treatment applications - Google Patents
A kind of thermally-stabilised, super-hydrophobic ceramic carbon nano-tube compound film and its membrane distillation water treatment applications Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
A kind of thermally-stabilised, super-hydrophobic ceramic carbon nano-tube compound film and its membrane distillation water treatment applications, it belongs to the technical field of inoranic membrane.The preparation of the composite membrane uses chemical vapour deposition technique, using ceramic hollow fibrous membrane as carrier, the different preparation condition by changing, such as catalyst loadings, reaction temperature and reaction time, structure, load capacity and the load condition of CNT are controlled, different structure and the ceramic CNT hollow fiber composite membrane of performance can be obtained.By the optimising and adjustment to preparation condition, the composite membrane that structure is completely covered in thermally-stabilised, super-hydrophobic CNT is obtained.The composite membrane can realize the efficient process of desalinization, high-salinity wastewater zero-emission and other waste water by membrane distillation（Such as electroplated heavy metals waste water, dyeing waste water and antibiotic waste water）, with good membrane distillation properties.
Description
Technical field
The present invention relates to the thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film of one kind and its membrane distillation water treatment applications, its
Belong to the technical field of inoranic membrane.
Background technology
Development and population explosion formula with global economy increase, and the demand to water resource is continuously increased.China is light per capita
Water is only the 1/4 of the world, is put into one of country of 13 most poor-waters in the world.Earth water money is only accounted for using freshwater resources
7th/100000th of source, and seawater accounts for 97.3%, therefore, it is also to meet industry in the future and raw at present that seawater and bitter alkali water desalination, which are,
The important selection of water demand living.Industrial high salt simultaneously from industrial process such as chemical industry, metallurgy, plating, oil and natural gas
Waste water（The waste water of total saliferous mass fraction at least 1%）In contain high concentration inorganic salts（Cl-、SO4 2-、Na+、Ca2+Deng）If, directly
Run in and put, also wasted water and salts resources while jeopardizing ecological environment, brine strength can not be too high in conventional treatment method, urgently
The zero discharge treatment technology of high-salt wastewater to be developed.Membrane seawater desalination be realize freshwater resources increase income increment main path it
One.Existing Membrane seawater desalination technology mainly has counter-infiltration（RO）, electrodialysis（ED）, pervaporation（PV）, multiple-effect evaporation
（MED）, multistage flash evaporation（MFS）And mechanical steam recompression（MVR）Deng.Although reverse osmosis technology is that seawater main at present is light
Change technology（It is ~ 70-90g/L to concentrate the upper limit）, operating cost is relatively low, but because the mesohaline rise of running can cause behaviour
The problems such as making pressure rise and fouling membrane, its concentrated water produced does not reach the level of direct industrial utilization still, can only directly arrange sea,
Otherwise environmental pollution can be caused, and counter-infiltration is not suitable for the desalination of high-salt wastewater.Electrodialysis（ED）Desalting efficiency even not
Foot, and because sea water conductivity is higher, cause current efficiency low, operating cost high energy consumption.In addition, electrodialysis easily causes electrolysis water
With the electrochemical corrosion of battery lead plate, the processing for high-concentration salt-containing wastewater also acquires a certain degree of difficulty（It is ~ 200g/L to concentrate the upper limit）.
Pervaporation（PV）It is a kind of technology suitable for high concentration desalinization, and ideal treatment effect, with being widely used in the Middle East
Area, but its operation temperature is higher, energy requirements amount is larger.Multiple-effect evaporation（MED）, multistage flash evaporation（MFS）And mechanical steam
Recompression（MVR）It there is investment and operating cost height and device not.
Membrane distillation（MD）The membrane separating process that membrane technology is combined with still-process, it using dewatering microporous film as medium,
In the presence of the vapour pressure deficit of film both sides, volatile component passes through fenestra in vapour form in feed liquid, so as to realize the mesh of separation
's.Compared with other separation processes, membrane distillation has that separative efficiency is high, operating condition is gentle, phase interaction film and material liquid
With and film mechanical property requirements it is not high the advantages of.Film distillation technology is that one kind can realize sea using low temperature exhaust heat or used heat
The membrane technology means of water, high concentration salt solution or sewage desalination, it can reach 100% recovery in theory, so as to realize haline water
Zero-emission.As low order waste heat is more and more paid attention to, solution route is provided for the energy consumption problem of film distillation technology, is made
Obtain application prospect of the membrane distillation in desalinization and high salt water treatment field further wide.For membrane distillation, the property of seperation film
Matter determines the effect and operation hours and cost of desalinization and high salt water process.First, distillation film needs to have good
Good hydrophobicity（Super-hydrophobicity is optimal）, it can so prevent liquid from entering fenestra road, and in solid liquid interface formation vapor film；Its
Secondary, distillation film need to possess high porosity and suitable membrane aperture (100-300nm) reduces membrane resistance, so that vapor is smoothly saturating
Cross film body and enter condensation side；Finally, distillation film also needs possess good physicochemical stability, temperature tolerance and resist wet and antipollution
Ability, it is ensured that it maintains good salt rejection rate and membrane flux in desalinization and high-salt wastewater processing procedure.At present, in the market
Distillation film be mainly organic polymer films, such as polypropylene (PP), Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE),
Such film there are problems that heat endurance, chemical stability it is not enough and, membrane structure and performance when causing longtime running
Decay in various degree, and commercial organic polymer films are not designed according to membrane distillation operating condition, its membrane distillation properties
Have much room for improvement.Therefore, exploitation has important available for the high-performance novel membrane material of desalinization and high-salt wastewater membrane distillation
Meaning.
At present, because ceramic membrane has, good chemical stability, antipollution, high temperature resistant, separative efficiency are high, easily regenerate and use
The advantages of long lifespan, the research of hydrophobically modified and the membrane distillation application of ceramic membrane has obtained certain progress, its hydrophobically modified side
Formula is mostly grafting silicon fluoride（FAS）, but heat endurance difference be its application technical bottleneck, FAS generally by covalent bond with
Ceramic membrane surface is combined, and because scission of link causes coming off for FAS molecules during long-term membrane distillation, causes the hydrophobicity of ceramic membrane to drop
It is low, cause film to infiltrate problem.Chemical field internal authority periodical AIChE Journal latest reports SiNCO inorganic nanos
The modified porous Si of grain3N4Ceramic membrane is used for membrane distillation desalination, compared with traditional silicon fluoride is modified, with similar hydrophobicity（Water
142 ° of contact angle）Higher heat endurance, but its membrane distillation properties is well below commercial polymer film, and preparation condition is relative
It is harsh（NH3Atmosphere, 600 °C of roastings）.Here, for the water treatment applications such as desalinization and high-salinity wastewater zero-emission, Wo Menfa
The porous ceramic film that a kind of Carbon nanotubes are modified is understood, with higher hydrophobicity（It is super-hydrophobic, water contact angle
170°）With good heat endurance, water treatment applications are realized by membrane distillation process.
CNT has good heat endurance and super-hydrophobicity, and resistance to strong acid, highly basic, less than 600 DEG C substantially not by
Oxidation, these features cause CNT to turn into a kind of excellent material of preparing or film modifier, for desalinization and high salt
The applications such as moisture film distillation.For existing membrane distillation CNT base seperation film, such as carbon nanotube polymer composite membrane and bar
Base paper film.Need first to aoxidize CNT in one side carbon nanotube polymer film film-forming process, to improve it in polymer
The dispersed degree of film, this reduces the hydrophobicity of CNT in itself, therefore prepared polymer-carbon nanotube film
The hydrophobic property of CNT is not given full play to, and its membrane distillation properties is undesirable.For Buckie paper membrane, although CNT
It is interlaced, flourishing high pore structure is formed, but CNT is to be loaded to by the mode of filtering on carrier, therefore carbon is received
Combination between mitron and carrier loosely easily comes off in application process, causes membrane structure and film properties to decay and secondary dirt
The problems such as dye.In consideration of it, providing the bond strength height between a kind of preferable supportive, CNT and carrier, can giving full play to
The advantages such as the super-hydrophobic of CNT, heat endurance and electric conductivity and the carbon nano-tube compound film material for being easy to prepare with scale,
And realize that its desalinization, high salt water zero discharge and other water process etc. are applied, have great importance.
Utilize chemical vapour deposition technique（CVD）Being capable of in-situ preparation of carbon nanotube and the good composite membrane of carrier binding ability
Material, can be effectively ensured the inherent characteristic of CNT, and structure, load capacity and the load condition of CNT are easy to by system
Standby parameter regulation and control.This method is in high temperature（600-800 °C）And atmosphere（Carbon-source gas, carrier gas）Under the conditions of carry out, therefore membrane carrier
Must possess the heat endurance of high temperature resistant and resistance to atmosphere.Compared with traditional organic polymer films, by the step of inversion of phases-sintering technology one
The hollow fiber ceramic membrane prepared is molded except with the high effective membrane area of loading density and unit volume, one-step shaping preparation
It is that a kind of high temperature is former with more characteristics such as high temperature resistant, heat endurance and chemical stability height outside the advantages such as anisotropic membrane structure
The most suitable membrane carrier of position load CNT.Meanwhile, ceramic hollow fibrous membrane has big finger-like pore and high porosity knot
Structure, can effectively reduce gas transfer resistance during CVD, and nucleation and the growing space of abundance are provided for CNT.Due to
Under different CVD preparation conditions, different structure and ceramics-CNT hollow fiber composite membrane of property can be obtained, especially
It is the structure, load capacity and load condition of CNT, and hydrophobicity, water and the gas flux of composite membrane and aperture etc..Cause
This, it is necessary to serial sign is carried out to the composite membrane prepared under different condition, so that the composite membrane of optimum structure and property is selected,
Obtain best membrane distillation properties.
Often containing materials such as hydrophilic humic acid, glycerine or natural organic matters in seawater and high-salt wastewater, it is in film
The attachment accumulation on surface often leads to film organic contamination, and the hydrophobicity on reduction film surface is to cause film to infiltrate and membrane distillation properties
The key factor of decline.In consideration of it, because CNT has good electric conductivity, the method aided in by electrochemistry can
The fouling membrane for the composite membrane that reduction CNT is completely covered, it is ensured that the membrane distillation properties of composite membrane.Because, in electrochemistry
Under subsidiary conditions, there is electrostatic force between pollutant and seperation film, add other mechanism of action that may be present, can press down
Attachment of the pollutant processed on film surface is accumulated, and reduces fouling membrane.
Further, carry out towards water treatment applications process ceramics-CNT hollow fiber composite membrane structure and
Property is designed, and can be extended to other water process according to its different film character water treatment applications different with performance progress
Using such as electroplated heavy metals waste water, dyeing waste water and antibiotic waste water etc..
The content of the invention
Present invention aims at provide a kind of high-performance carbon nanotube pottery with good heat endurance and super-hydrophobicity
Porcelain-carbon nano-tube compound film, desalinization, high-salinity wastewater zero-emission and other water treatment procedures are realized by membrane distillation process.
To achieve the above object, the present invention provides a kind of thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film, its film knot
Structure is that Carbon nanotubes are completely covered by spinelle hollow fiber ceramic membrane surface, i.e., what CNT was completely covered answers
Close film.Its pure water contact angle is 160-170 °, and liquid infiltration pressure is 2-2.5bar, and gas flux is 25-35m3·m-2·
h-1。
The preparation method for the composite membrane that the CNT is completely covered is as follows：
（1）10-20min will be soaked with washes of absolute alcohol as the spinelle hollow fiber ceramic membrane of carrier, then use pure water
Rinse, and in 60-70 DEG C of dry 1-2h, the spinelle hollow fiber ceramic membrane after being handled；
（2）By Ni (NO3)2The solution of 25-35% mass concentrations is configured to, the method coated with vacuum impregnation is by Ni (NO3)2Solution
It is coated on the carrier handled well, is placed in after 90-110 DEG C of dry 2-4h in Muffle furnace and is calcined 2-4h in 500-600 DEG C, born
Carry the spinelle hollow fiber ceramic membrane of NiO catalyst；
（3）The spinelle hollow fiber ceramic membrane for loading NiO catalyst is placed in crystal reaction tube, led into crystal reaction tube
Enter N2And H2In 500-550 DEG C of reducing catalyst 1-3h, the N2Flow velocity be 10-30ml/min, H2Flow velocity be 10-30ml/
min；650-680 DEG C of reaction temperature is then heated to, air-flow is switched to 20-30ml/min CH4, react after 3-5h, obtain
The composite membrane that CNT is completely covered.
Further, the pretreatment of the membrane carrier is that will be used as the anhydrous second of spinelle hollow fiber ceramic membrane of membrane carrier
Alcohol cleaning and dipping 10min, then with pure water rinsing, and in 60 DEG C of dry 1h, the membrane carrier handled well.It is described to prepare load
In the spinelle hollow-fibre membrane step of catalyst, Ni (NO3)2Solution is the solution that mass concentration is 30%.Concentration is too low, catalysis
The load capacity of agent is few, causes carbon nano tube growth amount less；Concentration is too high, it is fired after obtained nickel oxide particle size it is uneven
One, and nickel oxide particle is uneven in fibre pipe surface distributed, so as to cause the carbon nano tube growth of generation uneven.
The spinelle hollow-fibre membrane step for preparing supported catalyst is to use vacuum impregnation painting method by Ni (NO3)2
Solution is coated on the carrier handled well, is placed in after 100 DEG C of dry 2h in Muffle furnace and is calcined 2h in 500 DEG C, obtains load oxidation
The spinelle hollow-fibre membrane of Raney nickel.In the CVD reactions steps, N2、H2、CH4Flow all be 20ml/min.
The CVD reactions are that the spinelle hollow-fibre membrane of the load nickel oxide catalyst is placed in into crystal reaction tube
In, N is passed through into crystal reaction tube2And H2, 5 DEG C/min is warming up to 500 DEG C, and in 500 DEG C of reducing catalyst 1h, then 5 DEG C/
Min is warming up to 650 DEG C required of reaction temperature, and air-flow is switched into CH4The regular hour is reacted, air-flow is finally switched into N2,
Temperature fall, obtains the composite membrane that CNT is completely covered.The different reaction time can obtain the carbon nanometer of different structure
The composite membrane that pipe is completely covered, the reaction time is shorter, and carbon nano tube growth amount is less, obtains the compound of carbon nanotube portion covering
Film；Reaction time is longer, the increase of carbon nano tube growth amount, obtains the composite membrane that CNT is completely covered.
The different structure and the ceramics of performance obtained according to different preparation parameters-CNT hollow fiber composite membrane, it
There is different property, include load capacity, load condition, hydrophobicity, water and the gas flux and membrane aperture etc. of CNT.
It is 160-170 ° to possess pure water contact angle, and liquid infiltration pressure is 2-2.5bar, and gas flux is 25-35m3·m-2·h-1The composite membrane that is completely covered of CNT, with heat-staple super-hydrophobicity.It is compound that CNT is completely covered
Film utilizes the cheap energy such as various waste heats or used heat to be used for desalinization, aids in strengthening the antifouling property of film by electrochemistry.
It is used for the zero discharge treatment of high-salt wastewater using the cheap energy such as various waste heats or used heat, aids in strengthening the anti-of film by electrochemistry
Pollutant performance.It is used for concentration and the decontamination process of other waste water using the cheap energy such as various waste heats or used heat（As electroplated
Heavy metal wastewater thereby, dyeing waste water and antibiotic waste water etc.）Purposes.
1）The desalinization application for the composite membrane that CNT is completely covered
The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side（35g·L-1's
NaCl solution）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.Directly during contact film distilling seawater desalination,
The permeation flux of film is stable in 37 Lm-2·h-1Left and right, the rejection of salt more than 99%, and film during membrane distillation not
Can occur film wetting.
2）The high salt water zero discharge application for the composite membrane that CNT is completely covered
The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side（70g·L-1's
NaCl）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.In direct contact membranes still-process, the permeation flux of film
Stabilization is in 25 Lm-2·h-1Left and right, the rejection of salt is more than 99%.Therefore, the composite membrane that the CNT is completely covered has
Good high salt water treatment capacity.
The composite membrane that CNT is completely covered is when carrying out membrane distillation progress saline-water reclamation, and brine strength is more than or equal to
70g·L-1When, it can all realize the rejection of salt more than 99%.
3）High-salinity wastewater zero-emission application of the composite membrane that CNT is completely covered under electrochemistry subsidiary conditions
The composite membrane that CNT is completely covered is fixed on directly contact distillation device, and electrification is provided by dc source
Booster action is learned, applies 2V voltage.Composite membrane carries out membrane distillation, i.e. composite membrane as work electricity under the conditions of back bias voltage is applied
Pole, connects the negative pole of dc source；Titanium net connects the positive pole of dc source as to electrode.The hot water side of membrane distillation（70g·L-1's
NaCl and 30mg/L humic acid HA）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.In electrochemistry subsidiary conditions
Under（Back bias voltage）, the permeation flux stabilization of film is in 25 Lm-2·h-1Left and right, the rejection of salt shows that electrochemistry is auxiliary more than 99%
The pollution of film can be reduced by helping, and keep the membrane distillation properties relatively stablized.Therefore, CNT is aided in be completely covered by electrochemistry
Composite membrane there is good high-salt wastewater disposal ability, and can effectively prevent humic acid etc. from having under electrochemistry auxiliary
Pollution of the machine material to composite membrane.
The beneficial effect of the application：The carrier for the composite membrane that CNT is completely covered is the hollow fibre of spinelle porous ceramics
Film is tieed up, using CVD in-situ growing carbon nano tube, the composite membrane that CNT is completely covered is formed.Its pure water contact angle is
160-170 °, liquid infiltration pressure is 2-2.5bar, and gas flux is 25-35m3·m-2·h-1.With super-hydrophobicity and well
Heat endurance, desalinization, high-salinity wastewater zero-emission and other wastewater treatments can be realized by membrane distillation process.With ceramics
Hollow-fibre membrane is carrier, and its big straight-through finger aperture arrangement not only can guarantee that the lower resistance of various gases in chemical vapour deposition technique
Transmission, moreover it is possible to provide the space of abundance for the growth of CNT.Meanwhile, its high temperature resistant, resistant to chemical etching and high mechanical properties
It is also the basic demand directly by chemical vapor deposition for carbon nanotubes composite membrane, so that it is guaranteed that carbon etc. intrinsic advantages
Combination between nanotube and carrier, prevents CNT from being come off in application process, causes membrane structure to destroy and performance
Decay and secondary pollution problems.
The composite membrane that CNT is completely covered, the pore structure being mutually communicated with prosperity, high porosity, uniformly
Pore-size distribution, and with fabulous heat endurance and super-hydrophobicity, therefore can realize that desalinization, high salt are given up by membrane distillation
Water zero discharge and other wastewater treatment process, both with higher flux of membrane distillation, it may have the salt rejection rate more than 99%.Together
When, by electrochemistry booster action, the compound film process seawater and high-salt wastewater that CNT is completely covered have higher resist
Pollution capacity, obtains the flux of membrane distillation and salt rejection rate compared with high stable.Therefore, it can be prepared not by chemical vapour deposition technique
With structure and ceramics of different nature-CNT hollow fiber composite membrane, two kinds of different structure of composite membrane determine its hole
The difference of the performances such as footpath distribution, hydrophobicity, nitrogen flux, so as to which according to specific water treatment applications process, design is different
Structure of composite membrane, extend the application field of inoranic membrane.
The hydrophobicity and heat endurance for the composite membrane that CNT is completely covered are better than other ceramic film modifiers, such as fluorine silicon
Alkane and SiNCO.Therefore, its membrane distillation properties preferably, is not only mutually communicated network structure, and carbon nanometer with high porosity
Pipe has to vapor without friction transmission performance, it is ensured that the lower resistance transmission of vapor during membrane distillation, obtains more hypertonic
Saturating flux, while making full use of the good super-hydrophobicity of CNT, heat endurance and electric conductivity so that it has in membrane distillation mistake
There is long-term anti-wettability and contamination resistance well in journey, so that, in long-term membrane distillation operating process, exceeded
99% salt rejection rate and stable membrane distillation properties.
Using the structure, load capacity and load condition of the easily controllable CNT of chemical vapour deposition technique, by different
Operating condition can obtain the composite film material of different structure, different qualities, and different composite film materials can apply to difference
Water treatment procedure.The composite membrane of CNT s parts covering, relatively low hydrophobicity, therefore it is used for during membrane distillation easily
Film wetting is produced, is unfavorable for its membrane distillation application.And it has the network structure being mutually communicated, porosity is high, simultaneously because carbon
Nanotube has good electrochemical properties, therefore can filter oil-water emulsion by electric householder method, substantially reduces film dirty
Dye, improves the flux and the rejection to oil of film.
Brief description of the drawings
Fig. 1 is the pictorial diagram of spinelle doughnut membrane carrier.
Fig. 2 is the section low power stereoscan photograph of spinelle doughnut membrane carrier.
Fig. 3 is the pure water contact angle photo of spinelle doughnut membrane carrier.
Fig. 4 is the surface scan electromicroscopic photograph of the composite membrane of carbon nanotube portion covering in embodiment 1.
Fig. 5 is the surface scan electromicroscopic photograph of the composite membrane of carbon nanotube portion covering in embodiment 2.
Fig. 6 is the pure water contact angle photo of the composite membrane of carbon nanotube portion covering in embodiment 2.
The composite film surface stereoscan photograph that Fig. 7 is completely covered for CNT in embodiment 3.
The composite film surface stereoscan photograph that Fig. 8 is completely covered for CNT in embodiment 4.
The pure water contact angle photo for the composite membrane that Fig. 9 is completely covered for CNT in embodiment 4.
Figure 10 is to use membrane distillation properties of the composite membrane to seawater in embodiment 4.
Figure 11 is to use membrane distillation properties of the composite membrane to haline water in embodiment 4.
Figure 12 is the membrane distillation properties for using composite membrane high-salt wastewater under electrochemistry subsidiary conditions in embodiment 4.
Figure 13 is to use the fouling membrane situation that high-salt wastewater under membrane electrochemical subsidiary conditions is combined in embodiment 4（From a left side to
The right side is respectively：Open-circuit condition, back bias voltage, positive bias）.
Embodiment
The preparation of the composite membrane of the carbon nanotube portion of embodiment 1 covering
With spinelle hollow-fibre membrane as carrier, the composite membrane of carbon nanotube portion covering is prepared, step is：
The first step, will be used as the spinelle hollow fiber ceramic membrane of carrier（See Fig. 1）10min is soaked with washes of absolute alcohol, so
Pure water rinsing is used afterwards, and in 60 DEG C of dry 1h, the carrier handled well；
Second step, by Ni (NO3)2The solution of 30% mass concentration is configured to, the method coated with vacuum impregnation is by Ni (NO3)2It is molten
Liquid is coated on the carrier handled well, is placed in after 100 DEG C of dry 2h in Muffle furnace and is calcined 2h in 500 DEG C.Pass through X-ray diffraction
Instrument（XRD）Analysis is drawn a conclusion：This step obtains loading the spinelle hollow-fibre membrane of NiO catalyst.
3rd step, the spinelle hollow-fibre membrane for loading NiO catalyst is placed in crystal reaction tube, to crystal reaction tube
In be passed through N2And H2(flow is all 20ml/min) is urged in 500 DEG C of reduction the spinelle hollow-fibre membrane of load NiO catalyst
Agent 1h, then heats to 650 ° of reaction temperature, air-flow is switched to 20ml/min CH4, react after 15min, obtain carbon and receive
The composite membrane of nanotube segments covering.
As a result：Fig. 2 is the section low power stereoscan photograph of spinelle hollow fiber ceramic membrane, and the hollow-fibre membrane has
Asymmetric " Sanming City " controls structure, and close surfaces externally and internally is finger-like pore structure and center section is sponge Rotating fields, has tunica fibrosa
Have that high porosity, effective film thickness be small, resistance to mass tranfer is small and with good gas permeation flux and mechanical strength, so that
Be conducive to transmission of the carbon containing source of the gas between carrier layer, improve the yield of CNT；Fig. 3 is spinelle hollow fiber ceramic membrane
Pure water contact angle photo, it can be seen that its pure water contact angle is 17 °, therefore, and spinelle hollow fiber ceramic membrane has fine
Hydrophily.Fig. 4 is the surface scan electromicroscopic photograph for the composite membrane that carbon nanotube portion is covered.As can be seen that the reaction time is only
During for 15min, there are a large amount of ceramic monolith surfaces not covered by CNT.
The preparation of the composite membrane of the carbon nanotube portion of embodiment 2 covering
With spinelle hollow-fibre membrane as carrier, change the CVD reaction time, prepare the composite membrane of carbon nanotube portion covering,
Step is：
The first step, will soak 10min with washes of absolute alcohol as the spinelle hollow fiber ceramic membrane of carrier, then uses pure water
Rinse, and in 60 DEG C of dry 1h, the carrier handled well；
Second step, by Ni (NO3)2The solution of 35% mass concentration is configured to, the method coated with vacuum impregnation is by Ni (NO3)2It is molten
Liquid is coated on the carrier handled well, is placed in after 100 DEG C of dry 2h in Muffle furnace and is calcined 2h in 500 DEG C.
3rd step, the spinelle hollow-fibre membrane for loading NiO catalyst is placed in crystal reaction tube, to crystal reaction tube
In be passed through N2And H2(flow is all 25ml/min) is urged in 500 DEG C of reduction the spinelle hollow-fibre membrane of load NiO catalyst
Agent 1h, then heats to 650 ° of reaction temperature, air-flow is switched to 20ml/min CH4, reaction 45min after, obtain ceramics-
CNT hollow fiber composite membrane.As can be seen from Figure 5：Ceramic membrane surface part covers the structure of CNT.
As a result：Fig. 5 is the surface scan electromicroscopic photograph for the composite membrane that carbon nanotube portion is covered.As can be seen that due to anti-
45min is extended between seasonable, CNT largely covers ceramic monolith surface, CNT is not covered there is also part
Ceramic monolith.Fig. 6 is the pure water contact angle photo for the composite membrane that carbon nanotube portion is covered.Due to CNT have it is hydrophobic
Property, and ceramic monolith has hydrophily, therefore, the composite membrane of carbon nanotube portion covering has relatively low hydrophobicity, and pure water connects
Feeler is 102 °, and liquid infiltration pressure is 0.6bar, and gas flux is 56 m3·m-2·h-1, be not suitable for carrying out membrane distillation application.
The preparation for the composite membrane that the CNT of embodiment 3 is completely covered
With spinelle hollow-fibre membrane as carrier, the composite membrane that CNT is completely covered is prepared, step is：
The first step, will soak 10min with washes of absolute alcohol as the spinelle hollow fiber ceramic membrane of carrier, then uses pure water
Rinse, and in 60 DEG C of dry 1h, the carrier handled well；
Second step, by Ni (NO3)2The solution of 30% mass concentration is configured to, the method coated with vacuum impregnation is by Ni (NO3)2It is molten
Liquid is coated on the carrier handled well, is placed in after 100 DEG C of dry 2h in Muffle furnace and is calcined 2h in 550 DEG C.
3rd step, the spinelle hollow-fibre membrane for loading NiO catalyst is placed in crystal reaction tube, to crystal reaction tube
In be passed through N2And H2(flow is all 20ml/min) is urged in 500 DEG C of reduction the spinelle hollow-fibre membrane of load NiO catalyst
Agent 1h, then heats to 650 ° of reaction temperature, air-flow is switched to 20ml/min CH4, react after 2h, obtain ceramics-carbon
Nanotube hollow fiber composite membrane.
As a result：Fig. 7 is the composite film surface stereoscan photograph that CNT is completely covered.As can be seen that when reacted
Between be 2h when, the carbon nanotube network that ceramic surface is mutually communicated is completely covered, and the CNT film layer is shown
Flourishing is mutually communicated pore structure and porosity.
The preparation for the composite membrane that the CNT of embodiment 4 is completely covered
With spinelle hollow-fibre membrane as carrier, change CVD reaction time, prepare that CNT is completely covered is compound
Film, step is：
The first step, will soak 10min with washes of absolute alcohol as the spinelle hollow fiber ceramic membrane of carrier, then uses pure water
Rinse, and in 60 DEG C of dry 1h, the carrier handled well；
Second step, by Ni (NO3)2The solution of 30% mass concentration is configured to, the method coated with vacuum impregnation is by Ni (NO3)2It is molten
Liquid is coated on the carrier handled well, is placed in after 100 DEG C of dry 2h in Muffle furnace and is calcined 2h in 500 DEG C.
3rd step, the spinelle hollow-fibre membrane for loading NiO catalyst is placed in crystal reaction tube, to crystal reaction tube
In be passed through N2And H2(flow is all 20ml/min) is urged in 500 DEG C of reduction the spinelle hollow-fibre membrane of load NiO catalyst
Agent 1h, then heats to 650 ° of reaction temperature, air-flow is switched to 20ml/min CH4, react after 3h, obtain CNT
The composite membrane being completely covered.As can be seen from Figure 8：Carbon nanotube network is completely covered in ceramic membrane surface.
As a result：Fig. 8 is the composite film surface stereoscan photograph that CNT is completely covered.Fig. 9 is that CNT is complete
The pure water contact angle photo of the composite membrane of covering.As can be seen that when being 3h between when reacted, it is compound that CNT is completely covered
Film has higher super-hydrophobicity, and pure water contact angle is 170 °, and liquid infiltration pressure is 2bar, and gas flux is 30 m3·m-2·h-1.It therefore, it can by different preparation conditions, realize the controllable growth of ceramics-CNT hollow fiber composite membrane,
Obtain different structure and composite membrane of different nature.
The composite membrane that the CNT of embodiment 5 is completely covered is applied in the membrane distillation of desalinization
The desalinization application for the composite membrane that CNT is completely covered is carried out by directly contacting membrane distillation, step is：
The first step：The NaCl of certain mass is weighed, is added in pure water, concentration is configured to for 35gL-1NaCl solution be used as mould
The seawater of plan.
Second step：The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side
（35g·L-1NaCl solution）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.Pass through periodic detection cold water side matter
The change of amount, calculates the permeation flux of film.The electrical conductivity of penetrating fluid is determined using conductivity meter, salt rejection rate is calculated.Composite membrane
Run after 9h, carry out a hot water cleaning.
As a result show：Directly during contact film distilling seawater desalination, the permeation flux of film is stable in 37 Lm-2·h-1
Left and right, the rejection of salt is more than 99%, and stabilization time is more than 18h.Therefore, the ceramics-CNT hollow fiber composite membrane tool
There is stable film distilling seawater desalination performance, film wetting will not occur during membrane distillation for film.Figure 10 is that CNT is complete
Membrane distillation properties of the composite membrane of covering to seawater.
The high salt water zero discharge application for the composite membrane that the CNT of embodiment 6 is completely covered
The first step：The NaCl of certain mass is weighed, is added in pure water, concentration is configured to for 70gL-1NaCl solution be used as height
Salt solution.
Second step：The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side
（70g·L-1NaCl）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.Pass through periodic detection cold water side quality
Change, calculates the permeation flux of film.The electrical conductivity of penetrating fluid is determined using conductivity meter, salt rejection rate is calculated.Composite membrane is run
After 6h, a hot water cleaning is carried out.
As a result show：In direct contact membranes still-process, the permeation flux of film is stable in 25 Lm-2·h-1Left and right, salt
Rejection more than 99%.Therefore, the ceramics-CNT hollow fiber composite membrane has good high salt water treatment capacity, has
Prestige can realize high salt water zero discharge.Figure 11 is membrane distillation properties of the composite membrane that is completely covered of CNT to haline water.
The high salt water zero discharge application for the composite membrane that the CNT of embodiment 7 is completely covered
The first step：The NaCl of certain mass is weighed, is added in pure water, concentration is configured to for 150gL-1NaCl solution conduct
Haline water.
Second step：The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side
（150g·L-1NaCl）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.Pass through periodic detection cold water side quality
Change, calculate film permeation flux.The electrical conductivity of penetrating fluid is determined using conductivity meter, salt rejection rate is calculated.Composite membrane is transported
After row 6h, a hot water cleaning is carried out.
As a result show：In direct contact membranes still-process, the permeation flux of film is stable in 7.5 Lm-2·h-1Left and right, salt
Rejection more than 99%.Therefore, the ceramics-CNT hollow fiber composite membrane has good high salt water treatment capacity, has
Prestige can realize high salt water zero discharge.
High-salinity wastewater zero-emission of the composite membrane that the CNT of embodiment 8 is completely covered under electrochemistry subsidiary conditions should
With
The first step：The NaCl of certain mass is weighed, 30mg/L humic acid is added（HA）In solution, concentration is configured to for 70g
L-1NaCl and 30mg/L HA mixed solution be used as high-salt wastewater.
Second step：The composite membrane that CNT is completely covered is fixed on directly contact distillation device, passes through direct current
Power supply provides electrochemistry booster action, applies 2V voltage.Compare under three kinds of different conditions, the membrane distillation properties of composite membrane.One
For composite membrane in the open circuit condition（Do not apply voltage）Carry out membrane distillation.Two be that composite membrane carries out film under the conditions of back bias voltage is applied
Distillation, i.e., composite membrane connects the negative pole of dc source as working electrode；Titanium net connects the positive pole of dc source as to electrode.Three
Membrane distillation, i.e. composite membrane are carried out as working electrode under the conditions of positive bias is applied for composite membrane, connect the positive pole of dc source；Titanium
Net connects the negative pole of dc source as to electrode.The hot water side of membrane distillation（70g·L-1NaCl and 30mg/L HA）Temperature is
80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.By the change of periodic detection cold water side quality, the infiltration for calculating film is led to
Amount.The electrical conductivity of penetrating fluid is determined using conductivity meter, salt rejection rate is calculated.After composite membrane operation 6h, a hot water is carried out clear
Wash.
As a result show：In the open circuit condition, the permeation flux of film is gradually reduced, and the rejection of salt is more stable.This be because
For HA adheres in composite film surface, causes film surface contamination so that the flux reduction of film.After over cleaning, the flux of film is obtained
To recovery, illustrate that HA is weaker in the adhesive force of composite film surface.Under electrochemistry subsidiary conditions（Back bias voltage）, the permeation flux of film
Stabilization is in 25 Lm-2·h-1Left and right, the rejection of salt shows that electrochemistry auxiliary can reduce the pollution of film, kept more than 99%
Relatively stable membrane distillation properties.Because, HA shows electronegativity in water body, it means that between HA and the film for applying back bias voltage
Exist it is mutually exclusive, the effect reduce HA film surface accumulate, fouling membrane is reduced, so that the flux stablized.So
And, under electrochemistry subsidiary conditions（Positive bias）, the permeation flux of film is substantially reduced, after over cleaning, the permeation flux of film
Do not recover, and the rejection of salt is significantly reduced.Because, HA shows electronegativity in water body, it means that HA is with applying
Plus exist and attract each other between the film of positive bias, the effect enhances HA and accumulated on film surface, adds fouling membrane, so that
Obtaining the permeation flux and rejection of film constantly reduces.Therefore, aided in by electrochemistry, the ceramics-CNT doughnut is answered
Closing film has good high-salt wastewater disposal ability, is expected to that high-salinity wastewater zero-emission can be realized.
Figure 12 is the membrane distillation properties of high-salt wastewater under the compound membrane electrochemical subsidiary conditions that CNT is completely covered.Figure
13 be the fouling membrane situation of high-salt wastewater under the compound membrane electrochemical subsidiary conditions that CNT is completely covered.
The application for the compound film process heavy metal wastewater thereby that the CNT of embodiment 9 is completely covered
The application for the compound film process heavy metal wastewater thereby that CNT is completely covered, step are carried out by directly contacting membrane distillation
It is：
The first step：Prepare and contain Co2+、Cu2+、Ni2+And Mn2+Heavy metal wastewater thereby solution, each concentration of heavy metal ion be for
5mg·L-1。
Second step：The composite membrane that CNT is completely covered is fixed on directly contact distillation device, hot water side（Weight
Metallic wastewater）Temperature is 80 DEG C, cold water side（Deionized water）Temperature is 20 DEG C.By the change of periodic detection cold water side quality,
Calculate the permeation flux of film.The concentration of each heavy metal ion in penetrating fluid is determined using ICP-MS, rejection is calculated.Composite membrane is transported
After row 9h, a hot water cleaning is carried out.
As a result show：Directly during contact film distilling seawater desalination, the permeation flux of film is stable in 30 Lm-2·h-1
Left and right, the rejection of heavy metal is more than 99%, and stabilization time is more than 18h.Therefore, the composite membrane that the CNT is completely covered
With stable heavy metal containing wastewater treatment ability.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from the principle and objective of the present invention
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.
Claims (4)
1. a kind of thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film, it is characterised in that：The composite membrane is hollow with spinelle
Fiber ceramics film is carrier, and the composite construction of carrier is completely covered as membrane structure using CNT；The pure water contact of the composite membrane
Angle is 160-170 °, and liquid infiltration pressure is 2-2.5bar, and gas flux is 25-35m3·m-2·h-1；
The preparation method of the composite membrane is as follows：
（1）10-20min will be soaked with washes of absolute alcohol as the spinelle hollow fiber ceramic membrane of carrier, then use pure water
Rinse, and in 60-70 DEG C of dry 1-2h, the spinelle hollow fiber ceramic membrane after being handled；
（2）By Ni (NO3)2The solution of 25-35% mass concentrations is configured to, the method coated with vacuum impregnation is by Ni (NO3)2Solution
It is coated on the carrier handled well, is placed in after 90-110 DEG C of dry 2-4h in Muffle furnace and is calcined 2-4h in 500-600 DEG C, born
Carry the spinelle hollow fiber ceramic membrane of NiO catalyst；
（3）The spinelle hollow fiber ceramic membrane for loading NiO catalyst is placed in crystal reaction tube, led into crystal reaction tube
Enter N2And H2In 500-550 DEG C of reducing catalyst 1-3h, the N2Flow velocity be 10-30ml/min, H2Flow velocity be 10-30ml/
min；650-680 DEG C of reaction temperature is then heated to, air-flow is switched to 20-30ml/min CH4, react after 3-5h, obtain
The composite membrane that CNT is completely covered.
2. a kind of application of thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film according to claim 1, its feature exists
In：The composite membrane is applied in the membrane distillation of desalinization.
3. a kind of application of thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film according to claim 1, its feature exists
In：The composite membrane is applied to the high-salinity wastewater zero-emission in the membrane distillation of high-salinity wastewater zero-emission or under electrochemistry subsidiary conditions
In membrane distillation, the concentration of high-salt wastewater is more than or equal to 70g/L.
4. a kind of application of thermally-stabilised, super-hydrophobic ceramics-carbon nano-tube compound film according to claim 1, its feature exists
In：The composite membrane is applied in the membrane distillation of electroplated heavy metals waste water, dyeing waste water or antibiotic waste water.
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