CN109126462B - A kind of preparation method of the forward osmosis membrane for sea water desalination - Google Patents
A kind of preparation method of the forward osmosis membrane for sea water desalination Download PDFInfo
- Publication number
- CN109126462B CN109126462B CN201810975214.9A CN201810975214A CN109126462B CN 109126462 B CN109126462 B CN 109126462B CN 201810975214 A CN201810975214 A CN 201810975214A CN 109126462 B CN109126462 B CN 109126462B
- Authority
- CN
- China
- Prior art keywords
- bim
- mass percent
- osmosis membrane
- forward osmosis
- presoma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01D61/002—Forward osmosis or direct osmosis
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- 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
-
- 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
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation method of forward osmosis membrane for sea water desalination, steps are as follows: hydro-thermal method synthesizes Zn2(Po‑Bim‑OH)4Complex；To Zn2(Po‑Bim‑OH)4Presoma peels off to obtain Zn2(Po‑Bim‑OH)4Nanometer sheet；Hot drop coating embrane method preparation film forming, the aperture of the forward osmosis membrane is just the aperture of hydrone, and the water permeability of film, salt rejection rate is made to be largely increased compared to more traditional forward osmosis membrane.
Description
Technical field
The present invention relates to the preparation method of sea water desalination, it is related to a kind of system of the forward osmosis membrane of Non-energy-consumption for sea water desalination
Preparation Method.
Background technique
In China, no fresh water island accounts for about 92% or so of national island sum, and island, which is garrisoned, can only lean on naval vessels, ship etc.
Fresh water is transported, it is not only expensive but also laborious, sorrow of the harsh weather there are also water shortage is encountered, the maritime strategy safety of country has been seriously affected.
It is seen by the investigation result to 55 islands and 388 drinking water sources of 46 coastal areas, the fresh water sources master of officers and men stationed on the island
Lean on the reservoir water and sea water desalination of phreatic water, rainwater accumulation.Wherein the water of shallow layer surface water and reservoir water is by rainfall
Amount influences greatly, to be sometimes difficult to meet the drinking water needs of officers and men stationed on the island.Therefore sea water desalination is to solve current officers and men's drink stationed on the island
The effective way of problem of water consumption.
Seawater is a kind of extremely complex multicomponent aqueous solution.Various elements are all in the form of certain physical chemistry in seawater
In the presence of.The existence form of copper is complex in the seawater, is largely existing for organic complex form.In free ion only
With the presence of sub-fraction in the form of bivalent positive ion, most of is all with the appearance of anion complex compound.So free copper ion is only
Account for the sub-fraction of all dissolution copper.There is content sodium extremely abundant in seawater, but its chemical behavior is very simple, it is almost complete
Portion is with Na+Ionic species exists.Dissolved organic matter in seawater is sufficiently complex, mainly one kind object for being called " marine humus "
Matter, vegetation decomposes the humic acid generated and Fu Min acids seemingly in its property and soil.The molecular structure of marine humus does not have also
There is complete determination, but it and metal can form strong complex.According to the literature, the above substance can pass through forward osmosis membrane sea
Water desalination technology removes, to obtain drinkable fresh water.
Traditional desalination technology is broadly divided into 2 class of thermal method and embrane method, is developed so far the large-scale production work of comparative maturity
Skill technology mainly has 3 kinds: low temperature multiple-effect distillation technique (MED) and multi-stage flash process (MSF) and reverse osmosis seawater desalting work
Skill (RO).
Low temperature multiple-effect distillation technical operation temperature is low, the corrosion and scale problems of equipment can be effectively reduced, using cheap
Heat-transfer matcrial, using low level heat sources such as weary steam, industrial waste heats, system is high with the thermal efficiency, power consumption is small, operating flexibility
The advantages that big.But it is set because the reasons such as unstable, low efficiency of low temperature exhaust heat are much higher than the actual motion cost of the device
Cost is counted, while equipment volume is larger, installation cost is also higher.
Multistage flash distillation (MSF) is most widely used technique in thermal method, and operation temperature is mostly 110 DEG C~120 DEG C, equipment material
Material mostly uses the preferable stainless steel of corrosion resistance and corronil, and construction investment is high, generally uses the 2 of reverse osmosis technology engineering
Times.In addition, the operating flexibility of equipment is smaller, generally the 80%~110% of design value；Energy consumption is high, needs to combine with steam power plant
Operation.The scope of application: it is heat source to reduce operating cost that multi-stage flash evaporation technology, which generally utilizes the low level steam of power plant, is chiefly used in big
Type Seawater Desalination Project provides high-quality fresh water for coal-burning boiler, furthermore can also be used for domestic water.
Hyperfiltration (RO) sea water desalination belongs to membrane separation technique, which be applied more than to the water of reverse osmosis membrane side
The pressure of osmotic pressure, hydrone constantly penetrate reverse osmosis membrane using the selective penetrated property of reverse osmosis membrane, in going out for reverse osmosis membrane
Water side is finally flowed out in water outlet after collecting, and the impurity in intaking is trapped within the influent side of reverse osmosis membrane, then in concentrated water
Water outlet outflow.Reverse osmosis technology has many advantages, such as that high efficiency, low energy consumption, facility compact is beautiful, easily automatically controls.Currently, should
The most equipment of technological system has realized production domesticization, but the technology of high-pressure pump, energy recycle device and part membrane module is still located
In the stage of fumbling, equipment needs import.The membrane flux of film is more sensitive to temperature, when especially water temperature is low in winter, membrane flux meeting
It declines to a great extent.The domestic water that three of the above technique is suitable for officers and men's large area on island needs, and plant energy consumption is high, occupied area
Greatly.The features such as forward osmosis membrane technology is because of its low energy consumption, low pollution and high recycling uses potentiality very in fields such as sewage treatments
Greatly.Very big utilization is also obtained in fields such as power generation, Industrial Wastewater Treatment, food, space flight.
A kind of preparation of modified thin layer composite forward osmosis membrane of mineralising is disclosed in the patent of Publication No. CN107961682A
Method, this method have all obtained very big mention compared to traditional Cellulose acetate forward osmotic membrane in permeance property and selectivity
Height, but there are water fluxes it is small, salt rejection rate is low and pollution tendencies are big the disadvantages of.
A kind of alginic acid Pretreatment Technology of Seawater Desalination and its multiple is disclosed in the patent of Publication No. CN108178241A
Close salt fiber preparation, the preparation process is easier, and raw materials consumption is low, can further decrease desalination technology at
This.But this method desalting efficiency is low, water yield is small, cannot be applied on a large scale.
Summary of the invention
The purpose of the present invention is to overcome the disadvantages of the prior art, provides a kind of system of forward osmosis membrane for sea water desalination
Preparation Method, the preparation method simple possible, noenergy consumes in sea water desalination, and the film after handling is pollution-free, does not need clear
It washes and replaces, which contains the permeable site of a large amount of high activities, compared to the water penetration of film for more traditional forward osmosis membrane
Energy, salt rejection rate are greatly improved.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of the forward osmosis membrane for sea water desalination, comprising the following steps:
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) by mass percent be 0.5~1.5wt% polybenzimidazoles, mass percent be 0.1~0.85wt%'s
Dimethyl sulfoxide and mass percent are volume ratio addition three of the bromoethanol of 1~1.8wt% with 1:1:0.5~1:2:0.8
It in neck flask, using magnetic stirrer and flows back, obtains solid matter, be then washed with deionized, dry, obtain
To the modified polyphenyl containing hydroxyl and imidazoles；
(b) n,N-Dimethylformamide that mass percent is 5~8wt% is added to mass percent is 2~5wt%
Zn (NO3)·6H2In the solid mixture of O and modified polybenzimidazoles, in 600~1000 DEG C of autoclave
4~8h is calcined, is then stood at 22~25 DEG C, then be centrifuged recycling nanoparticle, the n,N-Dimethylformamide, Zn
(NO3)·6H2O, the volume mass ratio of modified polybenzimidazoles is 1ml:1ml:2g~1ml:2ml:2.5g；
(c) thoroughly clean nanoparticle with the methanol that percent by volume is 10~15%, by wet nanoparticle dry 20~
For 24 hours, drying obtains Zn under vacuum conditions2(Po-Bim-OH)4Presoma；
(2) to Zn2(Po-Bim-OH)4Presoma peels off to obtain Zn2(Po-Bim-OH)4Nanometer sheet, step are as follows:
(a) by Zn2(Po-Bim-OH)4Presoma is scattered in methanol and the mass percent that mass percent is 40~50%
It for 60~80% normal propyl alcohol in the mixed solvent, is sealed in ball grinder, the Zn2(Po-Bim-OH)4Presoma, methanol and just
The mass volume ratio of propyl alcohol is 1g:1ml:0.5ml~2g:1ml:2.5ml；
(b) ball grinder is fixed in the ball mill and mixture is small with the speed progress wet ball mill 1~2 of 60~80rpm
When；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 1~2 week in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet；
(3) hot drop coating embrane method preparation film forming, step are；
(a) by α-Al2O3Carrier disk washs in distilled water, is then transferred into third that mass percent is 70~80%
It is washed in ketone, dry 20~for 24 hours, then it is placed in 5~8h of preheating in heating plate, by the Zn of 2~5ml2(Po-Bim-OH)4Colloidal dispersions
It is coated uniformly in carrier disc surfaces, then with coating device in carrier disc surfaces, then dries, obtain Zn2(Po-Bim-OH)4It receives
Rice piece film；
(b) Zn is taken2(Po-Bim-OH)4The N that mass percent is 5~8wt% is added in conical flask in nanometer sheet film,
Dinethylformamide dissolution, magnetic stirrer form mixing emulsion, and mixing emulsion is then added to syringe
In, at 22~25 DEG C, the DC voltage of 10~50kV is added on syringe needle, leads to high pressure and carries out electrostatic spinning, obtained nanometer
The stainless steel drum of fiber ground connection is collected, and compound forward osmosis membrane is obtained.
Compared with prior art, the invention has the following advantages:
1. a pair polybenzimidazoles is modified processing, this method simple possible, significant effect introduces parent in the molecular structure
Aqueous hydroxyl group improves the hydrophilicity of polybenzimidazoles, makes it have high-hydrophilic.
2. this method can prepare aperture controllably (calcination temperature is different, and the aperture of nanoparticle is different), high-hydrophilic
Nanoscale forward osmosis membrane is discharged fast, it can be achieved that without the sea water desalination under the conditions of external energy, and salt rejection rate reaches 99.99%.
3. the forward osmosis membrane of this method preparation, Zn2(Po-Bim-OH)4Exist for a large amount of height is provided on forward osmosis membrane
Water penetration site, the aperture of the forward osmosis membrane are just the apertures of hydrone, and the water permeability of film, salt rejection rate is made to compare biography
System forward osmosis membrane is largely increased.
4. the method for the present invention not only Non-energy-consumption (driving for not needing electric energy, solar energy etc. can be carried out sea water desalination),
It is pollution-free；And water yield is big, salt rejection rate is high, and obtained purification water energy reaches the drinking water standard of national requirements, can be direct
It drinks.
Detailed description of the invention
Fig. 1 is the process flow chart that the present invention prepares forward osmosis membrane.
Specific embodiment
Below in conjunction with case study on implementation of the present invention, the technical solution in case study on implementation of the present invention is carried out clearly and completely
Description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
The preparation method of forward osmosis membrane proposed by the present invention for sea water desalination, comprising the following steps:
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) by polybenzimidazoles (Po-Bim) that mass percent is 0.5~1.5wt%, mass percent be 0.1~
The dimethyl sulfoxide and mass percent of 0.85wt% is the bromoethanol of 1~1.8wt% with the body of 1:1:0.5~1:2:0.8
Product using magnetic stirrer and flows back than being added in three-neck flask, obtains solid matter, be then washed with deionized water
It washs, dry, obtain the modified polyphenyl containing hydroxyl and imidazoles (Po-Bim-OH).
(b) by the n,N-Dimethylformamide (DMF) that mass percent is 5~8wt% be added to mass percent be 2~
Zn (the NO of 5wt%3)·6H2In the solid mixture of O and modified polybenzimidazoles, in 600~1000 DEG C of reaction under high pressure
4~8h is calcined in kettle, is then stood at 22~25 DEG C, then be centrifuged recycling nanoparticle, the n,N-Dimethylformamide,
Zn(NO3)·6H2O, the volume mass ratio of modified polybenzimidazoles is 1ml:1ml:2g~1ml:2ml:2.5g.
(c) thoroughly clean nanoparticle with the methanol that percent by volume is 10~15%, by wet nanoparticle dry 20~
For 24 hours, drying obtains Zn under vacuum conditions2(Po-Bim-OH)4Presoma.
(2) to Zn2(Po-Bim-OH)4(presoma is that have certain thickness layer structure to presoma, needs to carry out little by little
Removing obtain nanometer sheet) peel off obtain Zn2(Po-Bim-OH)4Nanometer sheet, step are as follows:
(a) by Zn2(Po-Bim-OH)4Presoma is scattered in methanol and the mass percent that mass percent is 40~50%
It for 60~80% normal propyl alcohol in the mixed solvent, is sealed in ball grinder, the Zn2(Po-Bim-OH)4Presoma, methanol and just
The mass volume ratio of propyl alcohol is 1g:1ml:0.5ml~2g:1ml:2.5ml；
(b) ball grinder is fixed in the ball mill and mixture is small with the speed progress wet ball mill 1~2 of 60~80rpm
When；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 1~2 week in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet.
(3) hot drop coating embrane method preparation film forming, step are；
(a) by α-Al2O3Carrier disk (commercially available) washs in distilled water, and being then transferred into mass percent is 70
It is washed in~80% acetone, dry 20~for 24 hours, then it is placed in 5~8h of preheating in heating plate, by the Zn of 2~5ml2(Po-Bim-
OH)4Colloidal dispersions coat in carrier disc surfaces (can use injector operations), then with coating device in carrier disc surfaces
It is even, it then dries, obtains Zn2(Po-Bim-OH)4Nanometer sheet film.
(b) Zn is taken2(Po-Bim-OH)4The N that mass percent is 5~8wt% is added in conical flask in nanometer sheet film,
Dinethylformamide (DMF) dissolution, magnetic stirrer form mixing emulsion.Then mixing emulsion is added to note
In emitter, at 22~25 DEG C, the DC voltage of 10~50kV is added on syringe needle, leads to high pressure and carries out electrostatic spinning, obtain
The stainless steel drum of nanofiber ground connection is collected, and compound forward osmosis membrane is obtained.
Embodiment 1
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) taking mass percent is polybenzimidazoles (Po-Bim) 10ml, the mass percent 0.1wt% of 0.5wt%
Dimethyl sulfoxide 10ml and mass percent be 1wt% bromoethanol 5ml be added three-neck flask in, using magnetic stirring apparatus
It stirs and flows back, obtain solid matter, be then washed with deionized, it is dry, obtain the modified polyphenyl containing hydroxyl simultaneously
Imidazoles (Po-Bim-OH).
(b) taking mass percent is that n,N-Dimethylformamide (DMF) 10ml of 5wt% is added to 10ml mass percent
For the Zn (NO of 2wt%3)·6H2In the solid mixture of the modified polybenzimidazoles of O and 20g, in 600 DEG C of reaction under high pressure
4h is calcined in kettle, is then stood at 22 DEG C, then is centrifuged recycling nanoparticle.
(c) nanoparticle is thoroughly cleaned with the methanol that percent by volume is 10%, by the dry 20h of wet nanoparticle, true
Drying obtains Zn under empty condition2(Po-Bim-OH)4Presoma.
(2) to Zn2(Po-Bim-OH)4Presoma peels off to obtain Zn2(Po-Bim-OH)4Nanometer sheet: 10gZn (a) is taken2(Po-
Bim-OH)4Presoma is scattered in the methanol that 10ml mass percent is 40% and the normal propyl alcohol that 5ml mass percent is 60% is mixed
In bonding solvent, it is sealed in ball grinder.
(b) tank is fixed in the ball mill, and mixture is carried out wet ball mill 1 hour with the speed of 60rpm；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 1 week in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet.
(3) hot drop coating embrane method preparation film forming
(a) by α-Al2O3Carrier disk (market purchase) washs in distilled water, and being then transferred into mass percent is
It is washed in 70% acetone, dry 20h.It is placed in heating plate and preheats 5h, with syringe by the Zn of 2ml2(Po-Bim-OH)4Colloid
It is scattered in carrier surface, then in α-Al2O3Disc surfaces uniformly coat, dry, obtain Zn2(Po-Bim-OH)4Nanometer sheet is thin
Film.
(b) Zn is taken2(Po-Bim-OH)4Nanometer sheet film is added the DMF dissolution of 20ml5wt%, uses magnetic force in conical flask
Blender stirs to form mixing emulsion.Mixing emulsion is added in syringe, at 22 DEG C, by the DC voltage of 10kv
It is added on syringe needle, leads to high pressure and carry out electrostatic spinning.Obtain nanofiber ground connection stainless steel drum collect, obtain it is compound just
Permeable membrane.
Compound forward osmosis membrane prepared by the present embodiment is placed in film properties evaluating apparatus, the seawater of 0.3mol/L is configured
For material liquid, the NH that liquid chooses 0.8mol/L is drawn4HCO3Solution.Experimental result is recorded after membrane module operation 5h, water flux is
80L/(m2H), salt rejection rate is up to 95%.Illustrate that compound forward osmosis membrane prepared by the present invention is had excellent performance, has higher
Water flux and salt rejection rate.
Embodiment 2
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) taking mass percent is polybenzimidazoles (Po-Bim) 10ml, the mass percent 0.85wt% of 1.5wt%
Dimethyl sulfoxide 20ml and mass percent be 1.8wt% bromoethanol 8ml be added three-neck flask in, using magnetic agitation
Device is stirred and is flowed back, and is obtained solid matter, is then washed with deionized, dry, obtains the modified polyphenyl containing hydroxyl
And imidazoles (Po-Bim-OH).
(b) taking mass percent is that n,N-Dimethylformamide (DMF) 10ml of 8wt% is added to 20ml mass percent
For the Zn (NO of 5wt%3)·6H2In the solid mixture of the modified polybenzimidazoles of O and 25g, in 1000 DEG C of reaction under high pressure
8h is calcined in kettle, is then stood at 23 DEG C, then is centrifuged recycling nanoparticle.
(c) nanoparticle is thoroughly cleaned with the methanol that percent by volume is 15%, wet nanoparticle is dry for 24 hours, true
Drying obtains Zn under empty condition2(Po-Bim-OH)4Presoma.
(2) to Zn2(Po-Bim-OH)4Presoma peels off to obtain Zn2(Po-Bim-OH)4Nanometer sheet:
(a) 20gZn is taken2(Po-Bim-OH)4Presoma is scattered in methanol and the 25ml matter that 10ml mass percent is 50%
The normal propyl alcohol in the mixed solvent that percentage is 80% is measured, is sealed in ball grinder.
(b) tank is fixed in the ball mill, and mixture is carried out wet ball mill 2 hours with the speed of 80rpm；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 2 weeks in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet.
(3) hot drop coating embrane method preparation film forming
(a) by α-Al2O3Carrier disk washs in distilled water, is then transferred into the acetone that mass percent is 80%
Washing, drying is for 24 hours.It is placed in heating plate and preheats 8h, with syringe by the Zn of 5ml2(Po-Bim-OH)4Colloidal dispersions are in carrier table
Face, then in α-Al2O3It is uniformly coated on disk, it is dry, obtain Zn2(Po-Bim-OH)4Nanometer sheet film.
(b) Zn is taken2(Po-Bim-OH)4Nanometer sheet film is added the DMF dissolution of 50ml8wt%, uses magnetic force in conical flask
Blender stirs to form mixing emulsion.Mixing emulsion is added in syringe, at 25 DEG C, by the DC voltage of 50kv
It is added on syringe needle, leads to high pressure and carry out electrostatic spinning.Obtain nanofiber ground connection stainless steel drum collect, obtain it is compound just
Permeable membrane.
Compound forward osmosis membrane prepared by the present embodiment should be placed in film properties evaluating apparatus, the sea of 0.5mol/L is configured
Water is material liquid, draws the NH that liquid chooses 1mol/L4HCO3Solution.Experimental result is recorded after membrane module operation 10h, water flux is
90L/ (m2h), salt rejection rate is up to 99%.Illustrate that compound forward osmosis membrane prepared by the present invention is had excellent performance, has higher
Water flux and salt rejection rate.
Embodiment 3
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) taking mass percent is polybenzimidazoles (Po-Bim) 10ml, the mass percent 0.15wt% of 0.8wt%
Dimethyl sulfoxide 12ml and mass percent be 1.2wt% bromoethanol 6ml be added three-neck flask in, using magnetic agitation
Device is stirred and is flowed back, and is obtained solid matter, is then washed with deionized, dry, obtains the modified polyphenyl containing hydroxyl
And imidazoles (Po-Bim-OH).
(b) taking mass percent is that n,N-Dimethylformamide (DMF) 10ml of 6wt% is added to 12ml mass percent
For the Zn (NO of 3wt%3)·6H2In the solid mixture of the modified polybenzimidazoles of O and 22g, in 800 DEG C of reaction under high pressure
5h is calcined in kettle, is then stood at 23 DEG C, then is centrifuged recycling nanoparticle.
(c) nanoparticle is thoroughly cleaned with the methanol that percent by volume is 12%, by the dry 22h of wet nanoparticle, true
Drying obtains Zn under empty condition2(Po-Bim-OH)4Presoma.
(2) to Zn2(Po-Bim-OH)4Presoma peels off to obtain Zn2(Po-Bim-OH)4Nanometer sheet:
(a) 12gZn is taken2(Po-Bim-OH)4Presoma is scattered in methanol and the 16ml matter that 10ml mass percent is 44%
The normal propyl alcohol in the mixed solvent that percentage is 65% is measured, is sealed in ball grinder.
(b) tank is fixed in the ball mill, and mixture is carried out wet ball mill 1.2 hours with the speed of 65rpm；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 1.2 weeks in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet.
(3) hot drop coating embrane method preparation film forming
(a) by α-Al2O3Carrier disk washs in distilled water, is then transferred into the acetone that mass percent is 75%
Washing, dry 22h.It is placed in heating plate and preheats 6h, with syringe by the Zn of 3ml2(Po-Bim-OH)4Colloidal dispersions are in carrier table
Face is coated uniformly on α-Al2O3It is on disk and dry, obtain Zn2(Po-Bim-OH)4Nanometer sheet film.
(b) Zn is taken2(Po-Bim-OH)4Nanometer sheet film is added the DMF dissolution of 45ml6wt%, uses magnetic force in conical flask
Blender stirs to form mixing emulsion.Mixing emulsion is added in syringe, at 23 DEG C, by the DC voltage of 20kv
It is added on syringe needle, leads to high pressure and carry out electrostatic spinning.Obtain nanofiber ground connection stainless steel drum collect, obtain it is compound just
Permeable membrane.
Compound forward osmosis membrane prepared by the present embodiment is placed in film properties evaluating apparatus, the seawater of 0.8mol/L is configured
For material liquid, the NH that liquid chooses 1.2mol/L is drawn4HCO3Solution.Experimental result is recorded after membrane module operation 10h, water flux is
85L/(m2H), salt rejection rate is up to 90%.Illustrate that compound forward osmosis membrane prepared by the present invention is had excellent performance, has higher
Water flux and salt rejection rate.
Embodiment 4
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) taking polybenzimidazoles (Po-Bim) 10ml, mass percent that mass percent is 1wt% is 0.65wt%'s
The bromoethanol 7ml that dimethyl sulfoxide 16ml and mass percent are 1.6wt% is added in three-neck flask, using magnetic stirring apparatus
It stirs and flows back, obtain solid matter, be then washed with deionized, it is dry, obtain the modified polyphenyl containing hydroxyl simultaneously
Imidazoles (Po-Bim-OH).
(b) taking mass percent is that n,N-Dimethylformamide (DMF) 10ml of 7wt% is added to 16ml mass percent
For the Zn (NO of 4wt%3)·6H2In the solid mixture of the modified polybenzimidazoles of O and 24g, in 900 DEG C of reaction under high pressure
7h is calcined in kettle, is then stood at 24 DEG C, then is centrifuged recycling nanoparticle.
(c) nanoparticle is thoroughly cleaned with the methanol that percent by volume is 14%, by the dry 23h of wet nanoparticle, true
Drying obtains Zn under empty condition2(Po-Bim-OH)4Presoma.
(2) to Zn2(Po-Bim-OH)4(presoma is that have certain thickness layer structure to presoma, needs to carry out little by little
Removing obtain nanometer sheet) peel off obtain Zn2(Po-Bim-OH)4Nanometer sheet:
(a) 16gZn is taken2(Po-Bim-OH)4Presoma is scattered in methanol and the 20ml matter that 10ml mass percent is 48%
The normal propyl alcohol in the mixed solvent that percentage is 70% is measured, is sealed in ball grinder.
(b) tank is fixed in the ball mill, and mixture is carried out wet ball mill 1.5 hours with the speed of 70rpm；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, to biggish unpeeled
Grain deposits 1.8 weeks in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet.
(3) hot drop coating embrane method preparation film forming
(a) by α-Al2O3Carrier disk (buying in market) washs in distilled water, is then transferred into mass percent and is
It is washed in 78% acetone, dry 23h.It is placed in heating plate and preheats 7h, with syringe by the Zn of 4ml2(Po-Bim-OH)4Colloid
It is scattered in carrier surface, is coated in α-Al2O3It is dry in disk, obtain Zn2(Po-Bim-OH)4Nanometer sheet film.
(b) Zn is taken2(Po-Bim-OH)4Nanometer sheet film is added the DMF dissolution of 46ml7wt%, uses magnetic force in conical flask
Blender stirs to form mixing emulsion.Mixing emulsion is added in syringe, at 24 DEG C, by the DC voltage of 40kv
It is added on syringe needle, leads to high pressure and carry out electrostatic spinning.Obtain nanofiber ground connection stainless steel drum collect, obtain it is compound just
Permeable membrane.
The controllable compound forward osmosis membrane in Non-energy-consumption prepared by the present embodiment, aperture is applied in sea water desalination experiment:
By this implement in the controllable compound forward osmosis membrane in prepared Non-energy-consumption, aperture be placed in film properties evaluating apparatus,
The seawater for configuring 1mol/L is material liquid, draws the NH that liquid chooses 1.5mol/L4HCO3Solution.Membrane module records in fact after running 10h
It tests as a result, water flux is 90L/ (m2H), salt rejection rate is up to 95%.Illustrate compound forward osmosis membrane prepared by the present invention
It can excellent, water flux with higher and salt rejection rate.
From the above experimental results, the compound forward osmosis membrane of Non-energy-consumption of this method preparation is had excellent performance, with higher
Water flux and salt rejection rate have good effect for sea water desalination.
Above specific embodiment has carried out specific description, but content of the present invention to method of the invention
Be not restricted to the above case study on implementation, if in without departing from main scope of the invention, can to experiment condition and method into
The flexible change of row, these are all within the scope of protection of the present invention.Therefore, the invention patent and protection scope should be with appended rights
Subject to claim.
Claims (1)
1. a kind of preparation method of the forward osmosis membrane for sea water desalination, it is characterised in that the following steps are included:
(1) hydro-thermal method synthesizes Zn2(Po-Bim-OH)4Complex:
(a) by mass percent be 0.5~1.5wt% polybenzimidazoles, mass percent be 0.1~0.85wt% diformazan
Base sulfoxide and mass percent are that the bromoethanol of 1~1.8wt% is burnt with volume ratio three necks of addition of 1:1:0.5~1:2:0.8
In bottle, using magnetic stirrer and flows back, obtain solid matter, be then washed with deionized, dry, contained
There are the modified polyphenyl and imidazoles of hydroxyl；
(b) n,N-Dimethylformamide that mass percent is 5~8wt% is added to the Zn that mass percent is 2~5wt%
(NO3)·6H2It stirs, is then stood at 22~25 DEG C, then be centrifuged in the solid mixture of O and modified polybenzimidazoles
Recycle nanoparticle, the n,N-Dimethylformamide, Zn (NO3)·6H2O, the volume mass of modified polybenzimidazoles
Than for 1ml:1ml:2g~1ml:2ml:2.5g；
(c) nanoparticle is thoroughly cleaned with the methanol that percent by volume is 10~15%, by wet nanoparticle dry 20~for 24 hours,
Drying obtains Zn under vacuum conditions2(Po-Bim-OH)4Presoma；
(2) to Zn2(Po-Bim-OH)4Presoma peels off to obtain Zn2(Po-Bim-OH)4Nanometer sheet, step are as follows:
(a) by Zn2(Po-Bim-OH)4Presoma is scattered in the methanol that mass percent is 40~50% and mass percent is 60
~80% normal propyl alcohol in the mixed solvent, is sealed in ball grinder, the Zn2(Po-Bim-OH)4Presoma, methanol and normal propyl alcohol
Mass volume ratio be 1g:1ml:0.5ml~2g:1ml:2.5ml；
(b) ball grinder is fixed in the ball mill, and mixture is carried out wet ball mill 1~2 hour with the speed of 60~80rpm；
(c) ball grinder is placed in ultrasonic bath and mixture is further peeled off, existed to biggish unpeeled particle
It is deposited 1~2 week in ball grinder, obtains Zn2(Po-Bim-OH)4The soliquid of nanometer sheet；
(3) hot drop coating embrane method preparation film forming, step are；
(a) by α-Al2O3Carrier disk washs in distilled water, is then transferred into the acetone that mass percent is 70~80%
Washing, dry 20~for 24 hours, then it is placed in 5~8h of preheating in heating plate, by the Zn of 2~5ml2(Po-Bim-OH)4Colloidal dispersions are in load
Body disc surfaces, then coated uniformly with coating device in carrier disc surfaces, it then dries, obtains Zn2(Po-Bim-OH)4Nanometer sheet
Film；
(b) Zn is taken2(Po-Bim-OH)4The N, N- bis- that mass percent is 5~8wt% is added in conical flask in nanometer sheet film
Methylformamide dissolution, magnetic stirrer form mixing emulsion, and then mixing emulsion is added in syringe,
At 22~25 DEG C, the DC voltage of 10~50kV is added on syringe needle, leads to high pressure and carries out electrostatic spinning, obtained nanofiber is used
The stainless steel drum of ground connection is collected, and compound forward osmosis membrane is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810975214.9A CN109126462B (en) | 2018-08-24 | 2018-08-24 | A kind of preparation method of the forward osmosis membrane for sea water desalination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810975214.9A CN109126462B (en) | 2018-08-24 | 2018-08-24 | A kind of preparation method of the forward osmosis membrane for sea water desalination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109126462A CN109126462A (en) | 2019-01-04 |
| CN109126462B true CN109126462B (en) | 2019-09-13 |
Family
ID=64827934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810975214.9A Active CN109126462B (en) | 2018-08-24 | 2018-08-24 | A kind of preparation method of the forward osmosis membrane for sea water desalination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109126462B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338072A (en) * | 2008-08-15 | 2009-01-07 | 同济大学 | Organic/inorganic composite enhancement type anhydrous proton conducting film and method for preparing same |
| CN105032201A (en) * | 2009-08-24 | 2015-11-11 | Oasys水有限公司 | Forward osmosis membranes |
| CN105056768A (en) * | 2015-09-15 | 2015-11-18 | 北京林业大学 | Hydrotalcite-similar composite forward osmosis membrane supporting layer and preparation method thereof |
| CN106397651A (en) * | 2016-11-08 | 2017-02-15 | 华东理工大学 | Composite forward osmosis membrane, method for preparing same and application of composite forward osmosis membrane |
-
2018
- 2018-08-24 CN CN201810975214.9A patent/CN109126462B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338072A (en) * | 2008-08-15 | 2009-01-07 | 同济大学 | Organic/inorganic composite enhancement type anhydrous proton conducting film and method for preparing same |
| CN105032201A (en) * | 2009-08-24 | 2015-11-11 | Oasys水有限公司 | Forward osmosis membranes |
| CN105056768A (en) * | 2015-09-15 | 2015-11-18 | 北京林业大学 | Hydrotalcite-similar composite forward osmosis membrane supporting layer and preparation method thereof |
| CN106397651A (en) * | 2016-11-08 | 2017-02-15 | 华东理工大学 | Composite forward osmosis membrane, method for preparing same and application of composite forward osmosis membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109126462A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105056768B (en) | A kind of compound forward osmosis membrane supporting layer of houghite and preparation method thereof | |
| CN107376666B (en) | A kind of modified cellulose acetate film and the preparation method and application thereof | |
| CN101857320B (en) | Method for treatment of silk degumming wastewater and recovery of silk gum | |
| CN101659673B (en) | Processing technology for recovering and utilizing mother solution of glyphosate as resource | |
| CN102139982B (en) | Water purification and regeneration device based on rotary spray evaporation and application of device | |
| CN102597253A (en) | Process for economically manufacturing xylose from hydrolysate using electrodialysis and direct recovery method | |
| CN107117755A (en) | A kind of high ammonia-nitrogen wastewater processing and ammonia recovery system and its method | |
| CN100567156C (en) | Adopt ultra-filtration membrane to purify and reclaim the method and apparatus of silking dirt alkali | |
| CN101020918A (en) | Process of recovering lutein material from marigold fermenting and squeezing liquid and treating comprehensively | |
| CN101274947A (en) | Method for extracting lignosulphonate from sodium sulfite bamboo pulp waste liquor | |
| CN101648970B (en) | Pre-treatment method of membrane technology resource recovery of glyphosate mother solution | |
| CN105967999B (en) | A kind of submicron order terephthalic acid (TPA) calcium cleans preparation method | |
| CN102153635A (en) | Method for extracting microcystin-LR (Laboratory reagent) from blue-green algae in Taihu Lake | |
| CN109126462B (en) | A kind of preparation method of the forward osmosis membrane for sea water desalination | |
| CN108947809A (en) | A method of extracting simultaneously refining long-chain dicarboxylic acids from fermentation liquid | |
| CN105080935B (en) | A kind of garbage flying ash cement kiln synergic processing and recycling of water resource utilize system | |
| CN208104086U (en) | Liquid sofening treatment system is concentrated in landfill leachate | |
| CN106365251A (en) | Recovery method for starch syrup ion exchange material pressing water | |
| CN204509027U (en) | A kind of Halite water desalination system based on tubular membrane | |
| CN103015246A (en) | Method for comprehensively using pulping waste water by sulfite method | |
| CN109019987A (en) | A kind of efficient recycling method of dyeing waste water | |
| CN218435031U (en) | Metal surface treatment liquid recycling system | |
| CN206156876U (en) | Useless lye recovery system of chitin production | |
| CN114988438A (en) | Lithium carbonate circulation lithium extraction process | |
| CN208980341U (en) | A kind of system that acidic etching waste liquid prepares micron cuprous oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |