CN104759261B - A kind of titanic oxide nano compound material and its production and use - Google Patents
A kind of titanic oxide nano compound material and its production and use Download PDFInfo
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Abstract
The present invention relates to the titanium dioxide (TiO for adsorbing heavy metal2) nano composite material and its production and use.The preparation method of the present invention includes Hydrolyze method, hydro-thermal method, self-assembly method.The composite of the present invention is by nano-TiO2Load on micron-sized polymer fiber or particle, polymer plays a part of fixed nano particle, prevents it from assembling and control its nucleating growth, solves the problems, such as reunion, loss and the secondary pollution that thus brings of the nano particle in application process.The composite of gained has stronger adsorption capacity to the heavy metal ion in water, purification and processing available for heavy metal in industry and sanitary wastewater.In addition, the preparation method of the present invention is simple to operation, raw material is green, cheap and easy to get, cost is low；And prepared material is easy to be engineered to bulk material so as to form device to use, therefore have a extensive future.
Description
Technical field
The present invention relates to a kind of titanic oxide nano compound material and its production and use, more particularly to a kind of green
Be used for adsorb special titanic oxide nano compound material of heavy metal and its production and use.
Background technology
With the rapid development of economy, industrial wastewater largely discharges, heavy metal pollution Frequent Accidents, clean water resources are increasingly
Shortage, seriously constrain the sustainable development of society.Lead, cadmium, mercury are the most significant elements of bio-toxicity in heavy metal.Due to weight
Metal can accumulate in vivo, and be transmitted in food chain through biological concentration, concentration, to ecological environment and human health structure
Into serious threat.Currently used heavy metal containing wastewater treatment technology mainly has chemical precipitation method, ion-exchange, UF membrane
Method, absorption method and bioanalysis.
The advantages that absorption method is due to easy to operate, advantages of good adsorption effect, non-secondary pollution and gain great popularity.Nano material is to inhale
One of the most frequently used adsorbent in attached method, it, which adsorbs heavy metal, has following characteristics：（1）Nano-material surface atomicity is with chi
It is very little reduction and increased dramatically, there is higher activity because Atomic coordinate deficiency makes nanostructured many surface defects be present,
Easily combined and tended towards stability with other atoms, therefore nano material can mutually be tied with some metal ions in a manner of electrostatic interaction etc.
Close, show very strong adsorption capacity, and adsorption equilibrium can be reached within a short period of time；(2) nano-particle specific surface area is very
Greatly, there is bigger adsorption capacity than common sorbing material.
Report in terms of the preparation of nano particle and the adsorption applications of heavy metal ion is a lot, such as
CN102078792A, CN102275998A and CN101591044A disclose the preparation method of metal nano oxide particle, inhale
Heavy metal ion effect in attached waste water is preferable.Efficiency is caused to reduce even however, nano particle is easily reunited in application process
Inactivation, and be easy to run off in fixed bed applications, difficulty is brought to separation and recycling, while to ecological environment and the mankind
Health causes certain harm.If nano particle is fixed on certain base material by certain stronger active force, can make
Problem is resolved.However, the publication of this aspect is less.
CN102974316A and CN102974326A discloses a kind of nano silicon heavy metal absorbent, with nanometer two
Silica（SiO2）For matrix, GMA is used（GMA）By its functionalization, then pass through radical polymerization
Method, by the silica of functionalization（SiO2-GMA）Respectively with polybutyl methacrylate（PBMA）And modified cyclodextrin（Ac-β-
CD）Copolymerization, is prepared for SiO2- GMA/PBMA composites and SiO2- GMA/Ac- β-CD composites.The invention is by polymer
It is coated on SiO2- GMA surface, makes SiO2Particle diameter increases, and reduces agglomeration, improves the absorption property of heavy metal, ties
Fruit shows：SiO2- GMA/PBMA is to lead ion in water（Pb2+）Adsorption rate can reach 99%；SiO2- GMA/Ac- β-CD are to copper ion
（Cu2+）Adsorption rate can reach 97.5%.But the preparation method is complicated, and the particle diameter of composite is answered still in nano-scale range
It is still inevitable in be lost in and secondary pollution problem.
CN101574641A is prepared for CNT/sodium alginate heavy metal ion sorbing material using sol-gel process.
The invention first instills sodium alginate aqueous solution in carbon nano tube dispersion liquid, is prepared into sodium alginate/carbon nanotube sol, so
Colloidal sol is injected in calcium chloride water afterwards and obtains gel particle, finally obtains CNT/sea by solidification filtering post processing
Mosanom granular composite material, to Pb in sewage2+With good adsorption capacity.This method is simple, does not produce secondary pollution,
Environment-friendly, however, nano particle is dispersed in the surface and inside of polymer, the mass ratio of CNT and sodium alginate is 4:
1, cost is higher.
Nano titanium oxide（TiO2）It is a kind of excellent urge with surface-active is strong, stability is good, low cost and other advantages
Agent and adsorbent.How effectively to use it for adsorbing the heavy metal in waste water, there is important meaning for solving water pollution
Justice.
The content of the invention
An object of the present invention is to provide a kind of preparation method of the nano composite material of titanium dioxide, the preparation
Method includes Hydrolyze method, hydro-thermal method and self-assembly method.Preparation method provided by the invention is simple to operation, raw material is green, cheap
Be easy to get, cost it is low.
An object of the present invention also resides in the nano composite material for providing titanium dioxide made from a kind of the inventive method,
By strong interaction by nano-TiO2Fixed to surface of polymer material, polymer plays fixed nano particle, prevents it
Assemble and control the effect of its nucleating growth, so as to obtain special nano-micro structure, meanwhile, solve nano-TiO2In application process
In reunion, be lost in and the secondary pollution problem thus brought.
An object of the present invention also resides in the purposes for the nano composite material for providing the titanium dioxide, is applied to
Adsorb heavy metal.The composite of the present invention has stronger adsorption capacity to the heavy metal ion in water, available for industrial and
The purification and processing of heavy metal in sanitary wastewater.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of one of preparation method of titanic oxide nano compound material, comprises the following steps：
(1) polymeric material is uniformly dispersed in a solvent, adjusts the pH value of dispersion liquid；
(2) stirring is lower adds TiO 2 precursor solution；
(3) lower heating response is stirred；
(4) after reaction terminates, cooling, through filtering, washing, being drying to obtain target product.
Preferably, the mass ratio of the polymeric material, TiO 2 precursor and solvent is 1:0.2-4:50-200, example
Such as it is 1:0.5:70、1:1.5:100、1:2:55、1:4:150、1:3:180 etc..TiO 2 precursor contains in reaction system
TiO in amount and concentrations on product2The content of nano particle, pattern and distribution influence are very big.Keeping, other reaction conditions are constant
In the case of, as TiO 2 precursor concentration increases, TiO2Content increase, tend to be steady after a certain equilibrium valve is reached
It is fixed.After TiO 2 precursor concentration supersaturation, unnecessary amount can not combine with fibrin reaction completely, but molten
Solution is finally removed in reaction system in post processing by filtering；In addition, TiO 2 precursor concentration is bigger, instead
Should be faster, the TiO of generation2Particle is easily uneven and easily reunites, and therefore, the present invention sets polymeric material, titanium dioxide
The mass ratio of presoma and solvent is 1:0.2-4:50-200.Moreover, the TiO in product is obtained under this quality proportioning2Nanometer
Grain is superimposed in surface of polymer material more uniform distribution without forming continuous film or multilayer film, to retain TiO as far as possible2Nanometer
The surface area of particle, there is stronger adsorption capacity so as to ensure to make to be made composite.
Preferably, step (1) described solvent is water or the mixture of water and low mass molecule alcohol；The low mass molecule alcohol is preferably
C1-C6 alcohol, more preferably methanol, ethanol or propyl alcohol；
Preferably, described pH value is less than 6, for example, 1.5,3.0,4.5,5.6 etc..PH value is acidity, can control water
Speed is solved, so as to better control over TiO2Pattern.PH value is smaller, and reaction is slower.But due to consideration that polymeric material exists
Added acid concentration has degraded when larger, and therefore, the concentration of regulation pH value when institute acid adding is also unsuitable excessive, should typically be no more than
0.3mol/L.TiO 2 precursor hydrolysis generates TiO2The process of nano particle is as follows：
mTi4+(aq)+4mH2O(1)→mTi(OH)4(aq)+4mH+(aq) (1)
mTi(OH)4(aq)→mTiO2(s)+2mH2O(aq) (2)
Preferably, the mode of step (2) described addition is to be added dropwise.
Preferably, the temperature of step (3) described reaction be 50-120 DEG C, for example, 55 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 115
DEG C etc., the time of reaction is 2-12h, for example, 3h, 4.5h, 6h, 8h, 10h, 11.5h etc..
Preferably, step (4) described drying is natural drying at room temperature or is 30-50 DEG C in temperature, for example, 33 DEG C, 38
DEG C, 42 DEG C, 46 DEG C, 49 DEG C etc., dry at preferably 35-50 DEG C.
The two of a kind of preparation method of titanic oxide nano compound material, comprise the following steps：
(1) TiO 2 sol is prepared by TiO 2 precursor；
(2) by polymer in the TiO 2 sol obtained by step (1) dipping-suction filtration, obtain coating titanium dioxide in advance
The polymer of titanium；Before hydro-thermal reaction, TiO is coated in surface of polymer material in advance2Colloidal sol, make TiO2With polymeric material
Better contact with, and be advantageous in the reaction of later step (3) to better control over TiO2In cellulose surface nucleation and life
It is long；
(3) polymer of the advance titanium dioxide coating obtained by step (2) is immersed in the solution of TiO 2 precursor,
Isothermal reaction；
(4) after reaction terminates, room temperature is cooled to, filters, wash, be drying to obtain target product.
Preferably, the time of dipping is more than 1min in step (2), for example, 2min, 4min, 6min, 8min etc., preferably
For 3min-5min.
Preferably, the component of the solution of the TiO 2 precursor described in step (3) includes TiO 2 precursor, hydrochloric acid
And water, the volume ratio of three is 0.5-3:25:25, preferably 1:25:25.
Preferably, described reaction is carried out in a kettle；It is preferred that the temperature reacted is 50~100 DEG C, for example, 55 DEG C,
60 DEG C, 80 DEG C, 85 DEG C, 98 DEG C etc., the time of reaction is 2~6h, for example, 2.3h, 2.8h, 4h, 5.5h etc..
Preferably, step (4) described drying is natural drying at room temperature or is 30-50 DEG C in temperature, for example, 33 DEG C, 38
DEG C, 42 DEG C, 46 DEG C, 49 DEG C etc., dry at preferably 35-50 DEG C.
The three of a kind of preparation method of titanic oxide nano compound material, comprise the following steps：
(1) TiO 2 sol is prepared by TiO 2 precursor；
(2) by polymer in the TiO 2 sol obtained by step (1) dipping-suction filtration, obtain coating titanium dioxide in advance
The polymer of titanium；
(3) by present 60-80 DEG C of the polymer of the advance titanium dioxide coating obtained by step (2), for example, 63 DEG C, 68
DEG C, 72 DEG C, 76 DEG C, 79 DEG C etc., more than 5min, for example, 6min, 8min, 11min etc. are preheated at preferably 70 DEG C, is preferably
10min, then at 85-95 DEG C, more than 2min is dried at for example, 88 DEG C, 91 DEG C, 94 DEG C etc., preferably 90 DEG C, is preferably
5min, 2-4h, preferably 3h are boiled in water-bath；Preheating therein can make TiO2Colloidal sol first with cellulose fiber surface knot
Close, and be unlikely to come off in boiling part afterwards.It is also actually hydro-thermal reaction to be boiled in water, is formed in the process
TiO2Nano particle, equivalent to the hydro-thermal method of lower temperature, operated compared with hydro-thermal method easier；
(4) after reaction terminates, room temperature is cooled to, filters, wash, be drying to obtain target product.
In preparation method of the present invention, the TiO 2 precursor is tetrabutyl titanate, titanyl sulfate, isopropanol
One kind or two or more mixing in titanium or titanium tetrachloride.
The four of a kind of preparation method of titanic oxide nano compound material, comprise the following steps：
(1) titanium oxide dispersion or TiO 2 sol that surface carries electric charge are prepared；Adjust dispersion liquid or colloidal sol
Surface is positively charged when pH value is less than 6.8, and surface is negatively charged when adjusting the pH value of dispersion liquid or colloidal sol more than 6.8；
(2) electric charge modification is carried out to surface of polymer material, be allowed to the electric charge with titanium dioxide opposite charge；Wherein
Electric charge modification can be carried out with prior art；
(3) by the electrically charged polymeric material infiltration in surface obtained by step (2) in titanium oxide dispersion obtained by step (1)
Or in TiO 2 sol, stand, wash, be drying to obtain target product；It is preferred that time of repose is more than 5min, it is, for example,
8min, 11min, 18min, 25min, 36min etc., more preferably 10-30min.Dry temperature is not higher than 50 DEG C, also may be used
Drying at room temperature.
Nano-TiO2With ambisexuality, point of zero electric charge is about in PH=6.8；And cellulose fibre in water disperse after,
It is negatively charged in pH=2-12 boundary inner surfaces.Therefore, as long as by TiO2Nano particle aqueous solution adjusts PH<6.8 by positive and negative
Electrostatic charge attracts self assembly can to realize both combinations；And for other polymers material, traditional electrostatic can be passed through
Sucking method is realized, i.e. can use cationic polyelectrolyte（Diallyl dimethyl ammoniumchloride (PDDA)）In polymer
Material surface modifies positive charge, and negative electrical charge is modified in surface of polymer material with kayexalate (PSS).
The present invention is by nano-TiO2Surface of polymer material is fixed to by strong interaction, polymer plays fixation and received
Rice grain, prevent it from assembling and control the effect of its nucleating growth, so as to obtain special nano-micro structure.Nano particle is fixed
Heavy metal in the later absorption waste water of change, for solving reunion of the nano particle in application process, being lost in and thus bring
Secondary pollution problem there is important scientific meaning and actual application value, and prepared material be easy to be engineered it is blocking
Greenization and the efficient activity of material and technology can be achieved so as to forming device such as filter or other devices to use in shape material
It is unified.
In preparation method of the present invention, the polymeric material is natural macromolecular material；Preferably cellulose, fibre
Tie up the one kind or two or more mixture in plain derivative, lignin, chitosan, chitin, starch, alginic acid or marine alga salt；
Preferably, the pattern of the polymeric material is threadiness or graininess.
Titanic oxide nano compound material made from the method for the invention that the second object of the present invention provides, by 1-
20wt%, for example, 3wt%, 5wt%, 7wt%, 11wt%, 15wt%, 18wt% etc. titania nanoparticles and 80-99wt%, example
Such as formed for 82wt%, 85wt%, 89wt%, 92wt%, 96wt% polymeric material, nano particle with Ti-O-C covalent bonds or
The interaction of Electrostatic Absorption is fixed on surface of polymer material；The pattern of the polymeric material is threadiness or graininess.
The purposes for the titanic oxide nano compound material of the present invention that the third object of the present invention provides, is used it for
Heavy metal adsorption, it is preferred for Pb2+Absorption, further preferably be used for sewage in Pb2+Absorption.
Compared with the nano material of existing absorption heavy metal, the advantage of the invention is that：The present invention fixes nano material
Onto polymer fiber or particle, polymer plays a part of fixed nano particle, prevents it from assembling and control its nucleating growth,
So as to obtain special nano-micro structure, for solving reunion of the nano particle in heavy metal adsorption application, being lost in and thus band
The secondary pollution problem come has important practical significance；Raw material is natural macromolecular material, abundance, cheap and easy to get；And
And a small amount of TiO2Content can reach good adsorption effect, and cost is low, method is easy, embodies Green Chemistry meaning.
Brief description of the drawings
Fig. 1 is TiO in the embodiment of the present invention 12The surface scan electromicroscopic photograph of/cellulose composite material；
Fig. 2 is TiO in the embodiment of the present invention 12The thermogravimetric analysis figure of/cellulose composite material, for calculating composite
Middle TiO2Content.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
1) by commercially available cellulose fibre（CF）（1g）Disperse in water (150ml), the concentrated sulfuric acid is then slowly added dropwise
（2ml）, stir simultaneously；
2) titanyl sulfate is added dropwise dropwise in above-mentioned fiber dispersion（TiOSO4）(0.8ml), while continue to stir；
3) 70 DEG C of heating water baths 4 hours, are stirred simultaneously；
4) reaction finishes, and cools down, is then filtered by vacuum, the fiber filter cake after being filtered dry repeatedly is rinsed with deionized water, 40 DEG C
Dry, obtain TiO2/ cellulose fibre nano composite material.
The surface topography of composite, TiO are made for the present embodiment by Fig. 12Nano particle is in cellulose surface in uniform point
Dissipate；Fig. 2 is the thermogravimetric analysis that composite is made in the present embodiment, the results showed that TiO2Content be 3.1wt%.
Embodiment 2
1) by commercially available cellulose fibre（1g）Disperse in water (200ml), the concentrated sulfuric acid is then slowly added dropwise（4ml）, together
When stir；
2) TiOSO is added dropwise dropwise in above-mentioned fiber dispersion4(2.4ml), while continue to stir；
3) 90 DEG C of heating water baths 3 hours, are stirred simultaneously；
4) reaction finishes, and cools down, is then filtered by vacuum, the fiber filter cake after being filtered dry repeatedly is rinsed with deionized water, 40 DEG C
Dry, obtain TiO2/ cellulose fibre nano composite material.
Embodiment 3
1) by tetrabutyl titanate（15ml）It is dissolved in 15ml isopropanols, is then slowly dropped in 150ml water, stirs simultaneously
Mix；
2) 1ml nitric acid is added in above-mentioned solution, continues stirring 2 hours at room temperature, obtain TiO2Colloidal sol；
3) by cellulose fibre in above-mentioned TiO2Sol impregnation-suction filtration, makes cellulose fiber surface coat TiO in advance2It is thin
Film；
4) tetrabutyl titanate is taken（1ml）It is added to 50ml hydrochloric acid solution（25ml HCl+25ml water）In, stir 10min
Afterwards, have in pouring into the reactor of polytetrafluoroethyllining lining；
5) TiO will be coated in advance2Cellulose fibre immerse in above-mentioned precursor solution, reactor is sealed after 70 DEG C of perseverances
Heated 4 hours in incubator；
6) reaction finishes, and treats that calorstat temperature is cooled to room temperature, takes out reactor, reaction solution is filtered by vacuum, after being filtered dry
Filter cake repeatedly rinsed with deionized water, be dried in vacuo, obtain TiO2/ cellulose nano composite material.
Embodiment 4
1) isopropyl titanate（5g）It is added in 100ml aqueous solution of nitric acid（Containing 1ml68%HNO3）, it is stirred at room temperature 18 hours, obtains
TiO2Colloidal sol；
2) by cellulose fibre in above-mentioned TiO21min is infiltrated in colloidal sol, filters and filters off colloidal sol, fiber is then put into 70
10min in DEG C preheating oven, then 90 DEG C of dry 5min, most after being boiled in water-bath 3 hours；
3) reaction finishes, and treats that water-bath cooling to room temperature, fiber is filtered, dries, obtains TiO2/ cellulose is nano combined
Material.
Embodiment 5
1) by TiO commercially available 50mg2Nano particle is added in 100ml deionized waters, and regulation pH value is 3, ultrasonic disperse 1
Hour, obtain uniform and stable dispersion liquid；
2) the electronegative cellulose fibre in surface is immersed in above-mentioned dispersion liquid, stands 20min, deionized water rinsing
5min, TiO can be obtained after drying2/ cellulose composite material.
Embodiment 6
1) by TiO commercially available 30mg2Nano particle is added in 100ml deionized waters, and regulation pH value is 6, ultrasonic disperse 1
Hour, obtain uniform and stable dispersion liquid；
2) the electronegative cellulose fibre in surface is immersed in above-mentioned dispersion liquid, stands 10min, deionized water rinsing
10min, TiO can be obtained after drying2/ cellulose composite material.
Thermogravimetric analysis and adsorbance test are carried out to titanic oxide nano compound material made from embodiment 1-6.
Thermogravimetric analysis is carried out using method commonly used in the art.
It is as follows to adsorb weight testing method：Prepare 30mg/L Pb2+Solution pipettes 100ml additions in 250ml volumetric flask
In triangular flask, pH value is adjusted.TiO made from above-described embodiment is taken respectively2/ cellulose fibre nano composite material 50mg adds it
In, then bottle is placed on shaking table and shakes certain time.After filtering with microporous membrane, try to filter by Atomic Absorption Spectrometry
Pb in liquid2+Concentration, calculate adsorption capacity.
Heavy metal ion adsorbed amount and thermal gravimetric analysis results obtained by embodiment 1-6 are shown in Table 1.
Table 1
Table 1 is TiO in the embodiment of the present invention2Nano composite material and corresponding unit mass TiO2Adsorbance.Due to
TiO2The adsorbance of/cellulose composite material heavy metal is attributed to cellulose and TiO2Joint contribution, so unit mass
TiO2Adsorbance data analysis it is more complicated.
Whole calculating process is analyzed by taking embodiment 1 as an example below：If by CF and TiO2Both contributions individually separate
Consider, for adsorbance 12.1mg/g, CF maximum contribution is 3.3mg/g, and minimum contribution is 0, i.e. TiO2Minimum contribution be
12.1-3.3=8.8mg/g, maximum contribution 12.1mg/g, that is, TiO in composite2Adsorbance be 8.8~12.1mg/
G, and TiO2Content be 3.1wt%, therefore, unit mass TiO2Adsorbance be then 283.9~390.3mg/g.Other are implemented
The calculating of example 2~6 is same as Example 1.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (21)
1. a kind of preparation method of titanic oxide nano compound material, comprises the following steps：
(1) polymeric material is uniformly dispersed in a solvent, the pH value for adjusting dispersion liquid is less than 1.5, and adjusts pH value when institute
The concentration of acid adding is no more than 0.3mol/L；
(2) stirring is lower adds TiO 2 precursor solution；
(3) lower heating response is stirred；
(4) after reaction terminates, cooling, through filtering, washing, being drying to obtain target product；
Wherein, the mass ratio of the polymeric material, TiO 2 precursor and solvent is 1:0.2-4:50-200.
2. according to the method for claim 1, it is characterised in that step (1) described solvent is water or water and low mass molecule alcohol
Mixture.
3. according to the method for claim 2, it is characterised in that the low mass molecule alcohol is C1-C6Alcohol.
4. according to the method for claim 3, it is characterised in that the low mass molecule alcohol is methanol, ethanol or propyl alcohol.
5. according to the method for claim 1, it is characterised in that the mode of step (2) described addition is to be added dropwise.
6. according to the method for claim 1, it is characterised in that the temperature of step (3) described reaction is 50-120 DEG C, reaction
Time be 2-12h.
7. according to the method for claim 1, it is characterised in that step (4) described drying is for natural drying at room temperature or in temperature
Spend to dry at 30-50 DEG C.
8. according to the method for claim 7, it is characterised in that step (4) described drying is for natural drying at room temperature or in temperature
Spend to dry at 35-50 DEG C.
9. a kind of preparation method of titanic oxide nano compound material, comprises the following steps：
(1) TiO 2 sol is prepared by TiO 2 precursor；
(2) by polymer in the TiO 2 sol obtained by step (1) dipping-suction filtration, obtain advance titanium dioxide coating
Polymer；
(3) polymer of the advance titanium dioxide coating obtained by step (2) is immersed in the solution of TiO 2 precursor, constant temperature
Reaction；
(4) after reaction terminates, room temperature is cooled to, filters, wash, be drying to obtain target product；
Wherein, the component of the solution of the TiO 2 precursor described in step (3) includes TiO 2 precursor, hydrochloric acid and water,
The volume ratio of three is 0.5-3:25:25.
10. preparation method according to claim 9, it is characterised in that the time of dipping is more than 1min in step (2).
11. preparation method according to claim 10, it is characterised in that the time of dipping is 3min- in step (2)
5min。
12. preparation method according to claim 9, it is characterised in that TiO 2 precursor described in step (3) it is molten
In the component of liquid, the volume ratio of TiO 2 precursor, hydrochloric acid and water three is 1:25:25.
13. preparation method according to claim 9, it is characterised in that described reaction is carried out in a kettle.
14. preparation method according to claim 9, it is characterised in that the temperature of the reaction is 50~100 DEG C, reaction
Time be 2~6h.
15. preparation method according to claim 9, it is characterised in that step (4) described drying be natural drying at room temperature or
Dried at being 30-50 DEG C in temperature.
16. preparation method according to claim 15, it is characterised in that step (4) described drying is natural drying at room temperature
Or dried in the case where temperature is 35-50 DEG C.
17. a kind of preparation method of titanic oxide nano compound material, comprises the following steps：
(1) TiO 2 sol is prepared by TiO 2 precursor；
(2) by polymer in the TiO 2 sol obtained by step (1) dipping-suction filtration, obtain advance titanium dioxide coating
Polymer；
(3) polymer of the advance titanium dioxide coating obtained by step (2) is first preheated into more than 5min at 60-80 DEG C, then
More than 2min is dried at 85-95 DEG C, 2-4h is boiled in water-bath；
(4) after reaction terminates, room temperature is cooled to, filters, wash, be drying to obtain target product.
A kind of 18. any one of claim 1-17 titanic oxide nano compound materials made from methods described, it is characterised in that by
1-20wt% titania nanoparticles and 80-99wt% polymeric material composition, nano particle is with Ti-O-C covalent bonds
Or the interaction of Electrostatic Absorption is fixed on surface of polymer material；The pattern of the polymeric material is threadiness or particle
Shape.
19. the purposes of the titanic oxide nano compound material described in a kind of claim 18, it is characterised in that use it for a huge sum of money
Category absorption.
20. the purposes of titanic oxide nano compound material according to claim 19, it is characterised in that by the titanium dioxide
Titanium nanometer composite material is used for Pb2+Absorption.
21. the purposes of titanic oxide nano compound material according to claim 20, it is characterised in that by the titanium dioxide
The Pb that titanium nanometer composite material is used in sewage2+Absorption.
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| CN106031863B (en) * | 2015-03-18 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of adsorbing separation composite cellulosic membrane, preparation method and its usage |
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