CN108246120A - A kind of rear-earth-doped mesoporous silica hybridized film and preparation method thereof - Google Patents
A kind of rear-earth-doped mesoporous silica hybridized film and preparation method thereof Download PDFInfo
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- CN108246120A CN108246120A CN201810127463.2A CN201810127463A CN108246120A CN 108246120 A CN108246120 A CN 108246120A CN 201810127463 A CN201810127463 A CN 201810127463A CN 108246120 A CN108246120 A CN 108246120A
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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
- B01D71/027—Silicium oxide
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
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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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- 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
The present invention relates to a kind of for high-performance silicon dioxide hybridized film of high concentration seawater or brine waste desalting processing and preparation method thereof.This method is by rare earth doped in colloidal sol is synthesized, regulation and control organosilane precursors structures so as to prepare the mesoporous silica hybridized film that high-performance rare-earth adulterates, membrane aperture is below 0.60nm, salt ion in energy effectively catching seawater (waste water) has the infiltration evaporation desalting performance of high-throughput, high rejection at room temperature.The preparation process of this method is simple, easy to operate, with good repeatability, prepared hybridized film also has excellent long-time hydrothermal stability, especially suitable for the reluctant high concentration seawater of reverse osmosis membrane technology or brine waste, can meet heavy industrialization application requirement.
Description
Technical field
The present invention relates to a kind of high permeating flux, rear-earth-doped mesoporous silica hybridized film preparation method and its ooze
Vaporization desalination application thoroughly, belongs to technical field of membrane separation.
Background technology
With the rapid development of economy, the shortage of whole world freshwater resources have become for people it is increasingly deeply concerned the problem of, arid
Etc. extreme weathers, industrial pollution, the deterioration of the ecological environment etc. to cause shortage of fresh water situation increasingly severe.World Water money will be accounted for
The seawater of more than 99% source total amount carries out sea water desalting and has become one of important channel for solving water resources crisis.With biography
System hot method desalting technology compare, using hyperfiltration as representative membrane technology carry out sea water desalination, have it is with good investment, low energy consumption,
Pollution less, convenient operation and management the advantages that, it has also become the advanced important desalting technology in the whole world.Industrial reverse osmosis membrane is big absolutely at present
Most is organic film material, since mechanical stability caused by its intrinsic Swelling is poor, poor chemical stability, antibiosis
Object pollutant performance is poor, needs the shortcomings of high pressure (usual tens atmospheric pressure) energy consumption, limits its large-scale application, it is difficult to meet honest and clean
The efficient scale sea water desalination industrialization requirement objective of valency.Therefore, there is an urgent need to research and develop high performance sea water desalination membrane
Material is to promote Membrane seawater desalination industrial applications process.
There is nanoporous silica silicon fiml good mechanical stability, resistance to acid and alkali, heat-resistant stability, aperture can design regulation and control
The advantages that, it is widely studied, have potentially should in the fields such as gas separation, membrane catalytic reactor, infiltration evaporation in recent years
Use prospect.Such as Wijaya (Desalination, 2009,236：291-298) by SiO2Film carries out infiltration evaporation desalination test,
The highest permeation flux of the film is 3.0Kg m-2h-1, the rejection of NaCl is 97.0%.(the Industrial＆ such as Xu
Engineering Chemistry Research, 2016,55：2183-2190) synthesized using crane span structure organic silicon source presoma as
The organic silica film of base, when 70 DEG C of NaCl solutions using 0.2wt% is feeding liquids, which is 14.2Kgm-2h-1, NaCl rejections are up to 99.6%；When 25 DEG C of NaCl solutions using 3.5wt% is feeding liquids, permeation flux is only 3.8Kg m-2h-1, NaCl rejections are 99.5%, show the application prospect of preferable infiltration evaporation desalination.
But pure SiO2Film is since its surface is rich in Si-OH groups, in the real industrial application environment rich in vapor etc.
In, by destroying so as to cause bad stability, separating property drastically declines porous skeleton structure, can not realize infiltration selection
The unification of property and stability.In order to improve its hydrothermal stability and separating property, it is typically employed in SiO2It introduces and dredges in membrane bone frame
The methods of aqueous group (such as silane precursor of Si-C-C-Si bases), containing transition metal (Pd, Co, Ni) and its oxide,
To improve micropore SiO2The hydrothermal stability of film and infiltration evaporation desalting performance.Nevertheless, based under low temperature (or room temperature)
The mesoporous silica membrane material of infiltration evaporation desalination is carried out for feeding liquid with high concentration brine (NaCl solution of such as >=3.5wt%)
The research report of material is less, and especially high permeating flux and the membrane material of high rejection are urgently researched and developed at room temperature.
Invention content
For current SiO2The deficiency of Membrane seawater desalination desalting technology, as the permeation flux of room temperature lower film is low, stability
Difference etc., present invention aims at provide a kind of to have high-throughput, high rejection, Gao Wen at room temperature for infiltration evaporation desalination
Qualitatively mesoporous silica hybridized film and preparation method thereof.This method passes through rare earth doped element, design in colloidal sol is synthesized
The structure of organosilane precursors and regulation and control preparation condition prepare the mesoporous silica hybridized film of high-performance rare-earth doping.
The average pore size of the film is 0.60nm hereinafter, (the hydrated ion size of salt is all higher than salt ion in energy effectively catching seawater
0.60nm), and the film has many advantages, such as high separability energy (permeation flux and rejection), prolonged hydrothermal stability, special
Not Shi Yongyu the reluctant high concentration seawater of reverse osmosis membrane technology or brine waste, also carried for embrane method highly effective and safe desalination application
For new way.
The present invention provides a kind of rear-earth-doped mesoporous silica hybridized films, using organosilan as presoma, use
Sol-gal process prepares rear-earth-doped mesoporous silica hybridized film by mixing rare earth element in colloidal sol is synthesized.
Further, the rare earth element is one or more in La, Y, Ce, Nd, Eu, Gd, Tb, Yb, more preferably
For La and Y.
The present invention also provides the preparation method of the rear-earth-doped SiO 2 hybrid film, step can be specially：
(1) organosilane precursors are added in absolute ethyl alcohol, be vigorously stirred at room temperature 3~6 hours, it then will be upper
It states mixed liquor and rare-earth salts is added under the conditions of ice-water bath, be vigorously stirred 3~4 hours, acid is finally added dropwise under agitation
With the mixed solution of deionized water, continuously stir 3~12 hours, can obtain rear-earth-doped under the conditions of 45~75 DEG C of waters bath with thermostatic control
Silicon dioxide gel；
(2) silicon dioxide gel that step (1) obtains with absolute ethyl alcohol is diluted, then porous supporting body is immersed and is diluted
Dip-coating 15~30 seconds is carried out in colloidal sol afterwards, drying 12~24 hours in climatic chamber are put into, in 200~400 DEG C of Muffle furnaces
Middle roasting 1~6 hour；
(3) after repeating the above steps (2) 2~4 times, it can obtain rear-earth-doped mesoporous silica hybridized film.
Further, the synthetic ratio of the silicon dioxide gel is organosilane precursors：Rare-earth salts：Acid：Go from
Sub- water：Absolute ethyl alcohol=1：0.05~0.3：0.1~0.2：60~120：60~150 (molar ratios).
Further, the organosilane precursors for tetraethyl orthosilicate, 1,2-two (triethoxy silicon substrate) second
Alkane, 1,2-two (triethoxy silicon substrate) methane, 1, one or more mixing of 2-two (triethoxy silicon substrate) ethylene.
Further, the rare-earth salts is one of the chlorate (or nitrate) containing La, Y, Ce, Nd, Eu, Gd, Tb, Yb
Kind or a variety of mixing.
Further, the acid is hydrochloric acid, nitric acid.
Further, the porous supporting body is Al2O3、ZrO2、TiO2Etc. materials, the shape of porous supporting body can be with
For sheet, tubulose, hollow fiber, average pore size is 20~200nm.
The present invention also provides a kind of above-mentioned application of rear-earth-doped mesoporous silica hybridized film prepared, i.e., by two
Silica hybridized film carries out infiltration evaporation desalting processing to high concentration seawater or brine waste.Film is placed in infiltration evaporation test
In membrane module, the side of film is feeding liquid side, and opposite side is per-meate side, and operating pressure is normal pressure (0.1MPa), and per-meate side is taken out true
Empty to be extremely less than 100Pa, per-meate side steam is using liquid nitrogen condensation to glass cold-trap.The separating property of film is by permeation flux J (Kg m- 2h-1) and rejection Rej% two parameters evaluated：
The quality m that permeation flux J measures penetrating fluid to penetrate per membrane area A in unit interval t：J=m/At；
Rejection Rej% can pass through test feed side concentration CfWith per-meate side concentration CpTo calculate：Rej%=(Cf-Cp)/Cf
× 100%.Penetrating fluid intermediate ion concentration uses conductivity meter and ion chromatography.
Compared with prior art, beneficial effects of the present invention are：
The present invention provides a kind of high-performance silicon dioxide hydridization for being used for high concentration seawater or brine waste desalting processing
Film and preparation method thereof, the preparation process of this method is simple, easy to operate, has repeatability well, prepared silica
The average pore size of hybridized film is in 0.60nm hereinafter, the infiltration evaporation at room temperature with high-throughput, high rejection, high stability takes off
Salt performance.At room temperature to NaCl, Na2SO4、MgCl2、MgSO4The rejection of salting liquids is waited higher than more than 99.99%, and the film
There is long-time hydrothermal stability, also there is high separating property in high temperature and high salt solution and loop test.
Specific embodiment
In order to further describe the present invention, several specific implementation cases are shown below.These embodiments are only used for specifically
The description present invention, does not form the limitation to the present patent application claim.
Embodiment 1
(1) 1, the 2- of 4.6mL bis- (triethoxy silicon substrate) ethane is added in the absolute ethyl alcohol of 88.7mL, at room temperature
It is vigorously stirred 3 hours, then above-mentioned mixed liquor is added in the yttrium nitrate of 0.0902g and 0.3075g nitric acid under the conditions of ice-water bath
After being vigorously stirred 3 hours, a certain amount of nitric acid and the mixed solution of deionized water is added dropwise in lanthanum under agitation so that
1,2- bis- (triethoxy silicon substrate) ethane：Yttrium：Lanthanum：Nitric acid：Deionized water：The molar ratio of ethyl alcohol is 1：0.019：0.056：
0.15：80：120, it is continuously stirred under the conditions of 60 DEG C of waters bath with thermostatic control 6 hours, can obtain molar ratio La：Y=25：75 rare earth is mixed
Miscellaneous silicon dioxide gel；
(2) by tubulose Al of the average pore size for 200nm2O3Porous supporting body immersion dilutes the step after 10 times with absolute ethyl alcohol
Suddenly in the silicon dioxide gel obtained in (1), dip-coating is put into drying 12 hours in climatic chamber after 20 seconds, hollow in Muffle furnace
It is warming up at 350 DEG C and roasts 3 hours under gas atmosphere；
(3) after repeating the above steps (2) 4 times, the mesoporous silica hybridized film of the uniform La/Y doping in surface is can obtain,
The average pore size of film is about 0.58nm after tested；
(4) infiltration evaporation that the above-mentioned SiO 2 hybrid film prepared is investigated to film using infiltration evaporation experiment is salt
Energy.Respectively with deionized water, the NaCl of initial concentration 0.3wt%, 1.0wt%, 2.0wt%, 3.5wt%, 0.3wt%'s
Na2SO4、MgCl2、MgSO4Solution is feeding liquid, and the desalting performance of the film is tested at 25 DEG C of room temperature, the results are shown in Table 1.
The desalting performance for the SiO 2 hybrid film that La/Y is adulterated in 1. embodiment 1 of table
Embodiment 2-5
Keep silicon dioxide gel middle rare earth salt dopping content constant i.e. (La+Y)：The ratio of Si is 0.075：1 (mole
Than), change La：Y ratios, other preparation conditions are identical with example 1, can obtain a series of titanium dioxide of difference La/Y doping ratios
Silicon hybridization film (i.e. embodiment 2~5).NaCl solution using initial concentration as 3.5wt% is feeding liquid, is tested at 25 DEG C of room temperature
The infiltration evaporation desalting performance of these SiO 2 hybrid films, the results are shown in Table 2.
Difference La/Y adulterates the desalting performance of the SiO 2 hybrid film of ratio in 2. embodiment 2-5 of table
Embodiment 6-9
It keeps adulterating La in silicon dioxide gel：The molar ratio of Y is 25：75, change rare-earth salts doping (La+Y)：Si's
Ratio, other preparation conditions are identical with example 1, can obtain a series of SiO 2 hybrid film of difference La/Y dopings (i.e.
Embodiment 6~9).NaCl solution using initial concentration as 3.5wt% is feeding liquid, these titanium dioxides are tested at 25 DEG C of room temperature
The infiltration evaporation desalting performance of silicon hybridization film, the results are shown in Table 3.
The desalting performance of the SiO 2 hybrid film of difference La/Y dopings in 3. embodiment 6-9 of table
Comparative example
Rare-earth salts is added without in synthetic silica sol-process, other preparation conditions are identical with example 1, can obtain
Pure 1,2-two (triethoxy silicon substrate) ethane are the SiO 2 hybrid film of base.Using initial concentration as the NaCl solution of 3.5wt%
For feeding liquid, the infiltration evaporation desalting performance of the film is tested at 25 DEG C of room temperature, comparing result is shown in Table 3.
Embodiment 10-11
The calcination temperature of film in embodiment 1 is become into 200 DEG C and 400 DEG C (corresponding embodiments 10 and 11 respectively) respectively,
His preparation condition is identical with example 1, can obtain SiO 2 hybrid film prepared by different calcination temperatures.Using initial concentration as
The NaCl solution of 3.5wt% is feeding liquid, and the infiltration evaporation desalting performance of these films is tested at 25 DEG C, the results are shown in Table 4.
The desalting performance of SiO 2 hybrid film that in 4. embodiment 10-11 of table prepared by different calcination temperatures
Embodiment 12
The rare-earth salts adulterated in embodiment 1 is changed to chlorate or nitrate containing Ce, Nd, Eu, Gd, Tb, Yb respectively, acid
For corresponding hydrochloric acid or nitric acid, other preparation conditions are identical with example 1, can obtain the titanium dioxide sila of different rare earth salt doppings
Change film.NaCl solution using initial concentration as 3.5wt% is feeding liquid, and the infiltration evaporation that these films are tested at 60 DEG C is salt
Can, it the results are shown in Table 5.
The desalting performance of different rear-earth-doped SiO 2 hybrid films in 5. embodiment 12 of table
Embodiment 13
(1) by the organosilane precursors 1 in step (1) in embodiment 1,2-two (triethoxy silicon substrate) ethane are changed to
1,2-two (triethoxy silicon substrate) methane are mixed with absolute ethyl alcohol and are vigorously stirred at room temperature 6 hours, then by above-mentioned mixing
Liquid adds in yttrium nitrate and lanthanum nitrate under the conditions of ice-water bath, after being vigorously stirred 4 hours, is added dropwise under agitation a certain amount of
Nitric acid and deionized water mixed solution so that 1,2-two (triethoxy silicon substrate) methane：Yttrium：Lanthanum：Nitric acid：Deionized water：
The molar ratio of absolute ethyl alcohol is 1：0.019：0.056：0.20：120：90, it is small under the conditions of 45 DEG C of waters bath with thermostatic control to continuously stir 12
When, it can obtain molar ratio La：Y=25：75 rear-earth-doped silicon dioxide gel；
(2) above-mentioned silicon dioxide gel absolute ethyl alcohol is diluted 7.5 times, then the sheet that average pore size is 50nm
ZrO2/Al2O3Asymmetric porous supporting body is immersed in the colloidal sol after dilution, and it is small that dry 24 are put into climatic chamber after dip-coating 30s
When, it is warming up at 250 DEG C and roasts 6 hours under air atmosphere in Muffle furnace；
(3) after repeating the above steps (2) 2 times, it can obtain the mesoporous silica hybridized film of the uniform La/Y doping in surface；
(4) infiltration evaporation that the above-mentioned SiO 2 hybrid film prepared is investigated to film using infiltration evaporation experiment is salt
It can be with Long Time Thermal stability.Using the NaCl solution of 3.5~4.2wt% as simulated seawater feeding liquid, tested at 25~60 DEG C
The desalting performance of the film and temperature cycles stability.Test result shows to permeate up to its in the test process of 200 hours
Flux is above 9.0Kg m-2h-1, the rejection of NaCl maintains more than 99.99%.
Claims (9)
1. a kind of rear-earth-doped mesoporous silica hybridized film, which is characterized in that the mesoporous silica hybridized film is mixed
It is miscellaneous to have rare earth element, using organosilan as presoma, using sol-gal process by mixing rare earth element system in colloidal sol is synthesized
It is standby go out rear-earth-doped mesoporous silica hybridized film.
2. mesoporous silica hybridized film according to claim 1, which is characterized in that the rare earth element for La, Y, Ce,
It is one or more in Nd, Eu, Gd, Tb, Yb.
3. mesoporous silica hybridized film according to claim 2, which is characterized in that the rare earth element is La and Y.
4. a kind of preparation method of rear-earth-doped mesoporous silica hybridized film, which is characterized in that including the steps：
(1) organosilane precursors are added in absolute ethyl alcohol, be vigorously stirred at room temperature 3~6 hours, it then will be above-mentioned mixed
It closes liquid and rare-earth salts is added under the conditions of ice-water bath, be vigorously stirred 3~4 hours, acid is finally added dropwise under agitation and goes
The mixed solution of ionized water continuously stirs 3~12 hours under the conditions of 45~75 DEG C of waters bath with thermostatic control, can obtain rear-earth-doped two
Silica sol；
(2) silicon dioxide gel that step (1) obtains is diluted with absolute ethyl alcohol, after porous supporting body is then immersed dilution
Dip-coating 15~30 seconds is carried out in colloidal sol, drying 12~24 hours in climatic chamber is put into, is roasted in 200~400 DEG C of Muffle furnaces
It burns 1~6 hour；
(3) after repeating the above steps (2) 2~4 times, it can obtain rear-earth-doped mesoporous silica hybridized film.
5. preparation method according to claim 4, which is characterized in that according to the method described in claim 1, its feature exists
In the synthetic ratio molar ratio of the silicon dioxide gel is organosilane precursors：Rare-earth salts：Acid：Deionized water：It is anhydrous
Ethyl alcohol=1：0.05~0.3：0.1~0.2：60~120：60~150.
6. preparation method according to claim 4, which is characterized in that the organosilane precursors are orthosilicic acid tetrem
Ester, 1,2-two (triethoxy silicon substrate) ethane, 1,2-two (triethoxy silicon substrate) methane, 1,2-two (triethoxy silicon substrates)
One or more mixing of ethylene.
7. preparation method according to claim 4, which is characterized in that the acid is hydrochloric acid or nitric acid.
8. preparation method according to claim 4, which is characterized in that the porous supporting body for sheet, tubulose or in
The Al of hollow fiber shape2O3、ZrO2Or TiO2Material, average pore size are 20~200nm.
A kind of 9. preparation method of rear-earth-doped mesoporous silica hybridized film, which is characterized in that the mesoporous silica
Hybridized film is used for the infiltration evaporation desalting processing of high concentration seawater or brine waste.
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| CN109772180A (en) * | 2019-02-25 | 2019-05-21 | 江西师范大学 | A kind of silicon dioxide film and its preparation method and application of alkali earth metal doping |
| CN111097297A (en) * | 2019-12-30 | 2020-05-05 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and preparation method and application thereof |
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| CN109772180A (en) * | 2019-02-25 | 2019-05-21 | 江西师范大学 | A kind of silicon dioxide film and its preparation method and application of alkali earth metal doping |
| US20220176326A1 (en) * | 2019-05-27 | 2022-06-09 | Conopco, Inc., D/B/A Unilever | Fibre comprising organosilane for purification of liquids |
| CN111097297A (en) * | 2019-12-30 | 2020-05-05 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and preparation method and application thereof |
| CN111097297B (en) * | 2019-12-30 | 2021-10-26 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and application |
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