CN104624159B - Preparation method of nano-structure composite absorbing material and application thereof - Google Patents
Preparation method of nano-structure composite absorbing material and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of the preparation technology and the separation technology of materials, relates to a preparation method of a nano-structure composite absorbing material and particularly relates to a preparation method of a novel maleic-acid modified meso-porous silicon material and an application of selective rare-earth ions. The method adopts maleic-acid amide as modified ligand, and adopts high-specific-surface meso-porous silicon as a supporting material to prepare the composite modified material which can realize selective absorption and separation of the rare-earth ions in mineral waste water. The result shows that the modified meso-porous silicon material obtained by utilizing the preparation method has excellent selective absorbing performance of the rare-earth ions.
Description
Technical field
The invention belongs to material preparation technology and separation technology field, it is related to a kind of system of nanostructured composite adsorbing material
Preparation Method, the rare earth in more particularly, to a kind of new preparation method of maleic acid modified mesoporous silicon material and selectivity waste suction water
The application of ion.
Background technology
With the growth of society's green, low-carbon economy, rare earth element is because its irreplaceable property is in permanent magnet, fluorescence
Lamp, rechargeable battery, the industrial circle such as catalyst is widely applied, in particular with hybrid vehicle, wind turbine, tight
Gather a large amount of popularizations of type fluorescent lamp, while the usage amount increasing rare earth metal and price, create contain in a large number dilute in a large number
Earth elements and the garbage of other metallic elements.These garbages because containing a large amount of rare earth metals and other heavy metal elements,
Tend not to correctly be processed, created the environmental problems such as serious water pollution and air pollution.
2010, European Union will be in its important report Critical Raw Materials for the European
Rare earth is classified as raw material extremely in short supply in (2010) by Union.In the same year, USDOE (DOE) will be in its annual report
By Nd, five kinds of rare earth elements of Eu, Tb, Dy and Y are classified as following mid-term element the most in short supply.So, the demand of rare earth will be in future
A period of time in, still can constantly increase, due to the external rare earth of China rationally supply and sustainable, the sending out of low-carbon economy
Exhibition, the prediction world that we can affirm will further improve to rare earth demand very much, specifically weight wherein in short supply
Following demand of rare earth element Eu, Dy may increase by 700% and 2600% respectively.Need in the face of so huge rare earth
The amount of asking, as the leading exporter of global rare earth trade, the opportunity that this is China is also challenge, and we open except strengthening rare earth
Send out supervision, rational exploitation, reduce rapidly in the face of incident intrinsic rare earth resources, rare earth resources as valuable not
Renewable limited resource, Recent study personnel while attempting to look for new resource to replace rare earth, also constantly
Grind the recovering rare earth from the solid waste of rare earth that makes internal disorder or usurp, so that rare-earth trade can keep sustainable development.Reach so-called
" equilibrium problem ", that is, under any circumstance, the demand and supply of rare earth needs to keep balance, gradually attaches most importance to from mining and separation
Industry Model excessively become to produce and be recovered as key industry pattern, promote China's Rare-earth Industry sustainable development, make China from dilute
Native big country becomes rare earth power.
Mesoporous silicon material because its orderly mesoporous sequence, high specific surface area (≈ 1000m2g-1), high-altitude hold and very
Good biocompatibility and be widely used in chemical industry catalysis, absorption, the various aspects such as biosensor.
The development and application of the nanostructured composite adsorbing material that mesoporous silicon material is produced with high selectivity ligand binding are
Most one of research of captivation.It mainly has two aspect advantages：On the one hand utilize the suction of mesoporous silicon material high power capacity
Attached property, improves the adsorption capacity of material.On the other hand, high selectivity part is grafted onto mesoporous silicon face, using high selection
Property part the selectively acting of rare earth ion is improved with the defect to rare earth ion adsorptive selectivity difference for the mesoporous silicon material, be prepared into
Meet the high selection of adsorbing material, the demand of high rare earth capacity to nanostructured composite adsorbing material, have become as current suction
Fufen from etc. field study hotspot
Content of the invention
For Shortcomings in prior art, the invention provides one kind with maleic acid for ligand stock to mesoporous silicon material
Be modified and selectivity waste suction water in rare earth ion application, this composite modification material has specific to Heavy rare earth
Adsorption property and higher adsorption capacity.
The present invention is to realize above-mentioned technical purpose by following technological means.
A kind of preparation method of the nanostructured composite adsorbing material to the selective absorption of Heavy rare earth, by following step
Suddenly carry out：
(1) take cetyl trimethylammonium bromide (CTAB) to be dissolved in distilled water, keep mechanical agitation, the Deca in solution
Sodium hydrate aqueous solution；Deca tetraethyl orthosilicate (TEOS), after reaction terminates, filters, washing, calcining, obtains mesoporous silicon and receive
Rice corpuscles；
(2) the nanometer particle ultrasonic disperse obtaining step (1), in toluene solution, then falls to aaerosol solution
Enter 3- aminopropyl triethoxysilane (APTES), the lower 24h that flows back of nitrogen protection, filters, washing, is dried, obtains silane-modified Jie
Hole silicon nano；
(3) silane-modified nanometer material step (2) being obtained and maleic anhydride (MA), it is scattered in N, N-2- first
In base Methanamide (DMF), pyridine is added to form suspension, nitrogen protection is lower to react, and solution system is changed into rufous, filters, and does
Dry, obtain maleic acid modified mesoporous composite material, i.e. nanostructured composite adsorbing material.
Wherein, the concentration after step (1) CTAB is dissolved in water is 2.0～2.1g/L, the body of water, TEOS and sodium hydroxide solution
Long-pending ratio is 960:2:7, the concentration of sodium hydroxide solution is 2M.
In step (1), described reaction temperature is 80 DEG C, and the time is 2h；Described calcining heat is 550 DEG C, and calcination time is
6h.
Finally in whole mixed solution, the concentration of nanometer particle is 12.5～13.0g/L to step (2) gained,
APTES is 2 with the volume ratio of toluene:75.
Described in step (1) and step (2), washing is with washing with alcohol three times.
In step (3), concentration in DMF for the modified nanometer material is 16.5～17.0g/L；The concentration 23.0 of MA
～23.5g/L, pyridine is 1 with the volume ratio of DMF:60.
In step (3), under described nitrogen protection, the temperature of reaction is 50 DEG C, and the time is 3h.
Above-mentioned nanostructured composite adsorbing material is applied to the rare earth ion in adsorption recovery water sample, concrete grammar according under
State step to carry out.
(1) the various rare earth ion of quality such as accurately weigh is configured to storing solution.
(2) the nanostructured composite adsorbing material taking certain mass adds in the middle of the rare earth ion storing solution of certain volume,
As for 25 DEG C of absorption 6h in water bath chader.
(3) if initial rare earth ion solubility is C0, the rare earth ion after absorption is Ct, then the multiple adsorption material of nanostructured
Material adsorption capacity QtCan be calculated with equation 1.
W：Quality V of adsorbing material:Volume M of rare earth storing solution：The relative atomic mass of rare earth ion
Beneficial effects of the present invention：
(1) adopt high-specific-surface mesoporous material, drastically increase the adsorption capacity of material, and preparation process is simply easily grasped
Make.
(2) it is used maleic anhydride as part, compared with the part high with other prices, significantly reduce the life of material
Produce cost.
(3) several Heavy rare earths can be carried out efficiently using the nanostructure composite material absorption that the present invention obtains
, high-selectivity adsorption separate.
Brief description
Fig. 1：A () projects electron microscope for mesoporous silicon material projection electron microscope, (b) for nanostructured composite adsorbing material.
Fig. 2：Mesoporous silicon material, the FT-IR figure of nanostructured composite adsorbing material.
Fig. 3：Mesoporous silicon material, the thermal multigraph of nanostructured composite adsorbing material.
Fig. 4：Mesoporous silicon material, the nanostructured composite adsorbing material adsorption experiment figure to rare earth ion.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
Not limited to this.
Embodiment 1：
(1) 500mgCTAB, is dissolved in 240mL distilled water, keeps mechanical agitation, Deca 1.75mL hydrogen-oxygen after half an hour
Change sodium solution and 0.5mL TEOS.React 2h, centrifugation at 80 DEG C, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon materials 1g is dissolved in 75mL toluene.Deca 2mL APTES, flows back one day, obtains silicon
Alkane modification mesoporous silicon material.
(3) silane-modified for the 0.25g obtaining in (2) mesoporous silicon material is scattered in 15mL DMF, is subsequently adding 0.35g
Maleic anhydride (MA), 0.25mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system is changed into rufous.Filter, be dried, obtain
To maleic acid modified mesoporous composite material.
(5) mesoporous silicon material, the projection electron microscope of nanostructured composite adsorbing material is as shown in Figure 1.
(6) mesoporous silicon material, the FT-IR figure of nanostructured composite adsorbing material is as shown in Figure 2.In figure 1091 He
3432cm-1Being respectively at wave number is Si-O-Si asymmetrical stretching vibration, Si-OH stretching vibration.1650cm-1And 1550cm-1Ripple
At number, it is CO stretching vibration peak (amine I), NH deformation vibration (amine), show part in the success of mesoporous material surface modification.
(7) mesoporous silicon material, the thermal multigraph of nanostructured composite adsorbing material.As can be known from Fig. 3, less than 100 DEG C is to lose
Water, composite begins with obvious weightlessness from 150 DEG C, this is because surface success grafting part, modified success is described.
Embodiment 2：
(1) 400mgCTAB, is dissolved in 200mL distilled water, keeps mechanical agitation, Deca 1.45mL hydrogen-oxygen after half an hour
Change sodium solution and 0.414mL TEOS.React 2h, centrifugation at 80 DEG C, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon materials 2.06g is dissolved in 160mL toluene.Deca 4.267mL APTES, backflow one
My god, obtain silane-modified mesoporous silicon material.
(3) silane-modified for the 0.32g obtaining in (2) mesoporous silicon material is scattered in 20mL DMF, is subsequently adding 0.46g
Maleic anhydride (MA), 0.333mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system is changed into rufous.Filter, be dried,
Obtain maleic acid modified mesoporous composite material.
(5) mesoporous silicon material, the projection electron microscope of nanostructured composite adsorbing material is as shown in Figure 1.Show very in Fig. 1
Substantially ordered mesoporous pore canals structure.
(6) mesoporous silicon material, the FT-IR figure of nanostructured composite adsorbing material is as shown in Figure 2.In figure 1091 He
3432cm-1Being respectively at wave number is Si-O-Si asymmetrical stretching vibration, Si-OH stretching vibration.1650cm-1And 1550cm-1Ripple
At number, it is CO stretching vibration peak (amine I), NH deformation vibration (amine II), show part in the success of mesoporous material surface modification.
(7) mesoporous silicon material, the thermal multigraph of nanostructured composite adsorbing material.As can be known from Fig. 3, modified success
(8) the nanostructured composite adsorbing material of preparation is used for the separation adsorption experiment of rare earth ion.
Take rare earth ion to be configured to a series of 20mg/L aqueous solutions and be configured to standard reserving solution.20mg nanostructured is taken to be combined
Adsorbing material is added in 10mL color comparison tube, 25oC concussion uniformly, detects remaining rare earth ion concentration using ICP-OES.
Test result is as shown in Figure 4.Wherein dissociation constant Kd,
C0For rare earth ion initial concentration, C is rare earth ion equilibrium concentration, and V is the volume (mL) of solution, and m is adsorbent
Quality (mg).
Result shows, nanostructured composite adsorbing material has very high adsorption capacity and very strong selection to Gd ion
Property, dissociation constant reaches 342, can be used for the adsorbing separation to rare earth ion and reclaim.
Embodiment 3：
(1) 201.6mg CTAB, is dissolved in 96mL distilled water, keeps mechanical agitation, Deca 0.7mL hydrogen-oxygen after half an hour
Change sodium solution and 0.2mL TEOS.React 2h, centrifugation at 80 DEG C, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon material 1.3g is dissolved in 100mL toluene.Deca 2.667mL APTES, flows back one day,
Obtain silane-modified mesoporous silicon material.
(3) silane-modified for the 0.425g obtaining in (2) mesoporous silicon material is scattered in 25mL DMF, is subsequently adding
0.587g maleic anhydride (MA), 0.417mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system is changed into rufous.Filter,
It is dried, obtain maleic acid modified mesoporous composite material.
Described embodiment be the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment, not
In the case of deviating from the flesh and blood of the present invention, any conspicuously improved, replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (6)
1. a kind of preparation method of nanostructured composite adsorbing material is it is characterised in that follow the steps below：
(1) take cetyl trimethylammonium bromide CTAB to be dissolved in distilled water, keep mechanical agitation, the Deca hydroxide in solution
Sodium water solution, Deca tetraethyl orthosilicate TEOS, after reaction terminates, filters, washing, calcining, obtains nanometer particle；
(2) the nanometer particle ultrasonic disperse obtaining step (1), in toluene solution, then pours 3- into aaerosol solution
Aminopropyl triethoxysilane APTES, the lower 24h that flows back of nitrogen protection, filter, washing, are dried, obtain silane-modified mesoporous silicon and receive
Rice corpuscles；Finally in whole mixed solution, the concentration of nanometer particle is 12.5～13.0g/L, APTES and toluene to gained
Volume ratio be 2:75；
(3) silane-modified nanometer material step (2) being obtained and maleic anhydride MA, it is scattered in N, N- dimethyl formyl
In amine DMF, pyridine is added to form suspension, nitrogen protection is lower to react, and solution system is changed into rufous, filters, and is dried, obtains horse
Come sour modification mesoporous composite material, i.e. nanostructured composite adsorbing material；Concentration in DMF for the modified nanometer material is
Concentration 23～the 23.5g/L of 16.5～17g/L, MA；Pyridine is 1 with the volume ratio of DMF:60.
2. a kind of nanostructured composite adsorbing material according to claim 1 preparation method it is characterised in that：Step
(1) in, the concentration after CTAB is dissolved in water is 2.0～2.1g/L, and the concentration of sodium hydroxide solution is 2M；Water, TEOS and hydroxide
The volume ratio of sodium solution is 960:2:7.
3. a kind of nanostructured composite adsorbing material according to claim 1 and 2 preparation method it is characterised in that：Step
Suddenly in (1), described reaction temperature is 80 DEG C, and the time is 2h；Described calcining heat is 550 DEG C, and calcination time is 6h.
4. a kind of preparation method of nanostructured composite adsorbing material according to claim 1 is it is characterised in that described step
Suddenly washing described in (1) and step (2) is with washing with alcohol three times.
5. a kind of preparation method of nanostructured composite adsorbing material according to claim 1 is it is characterised in that step
(3), in, under described nitrogen protection, the temperature of reaction is 50 DEG C, and the time is 3h.
6. a kind of preparation method of nanostructured composite adsorbing material according to claim 1 is it is characterised in that prepared
Nanostructured composite adsorbing material be applied to the adsorbing separation of rare earth ion is reclaimed.
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| CN109433160B (en) * | 2018-11-28 | 2021-04-30 | 常州大学 | Preparation method and application of diammine bridge mesoporous hybrid silicon adsorbent |
| CN110038537A (en) * | 2019-04-15 | 2019-07-23 | 云南大学 | A kind of modified Nano porous silicon adsorbent and the preparation method and application thereof |
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| CN104046805A (en) * | 2014-06-27 | 2014-09-17 | 武汉工程大学 | Method for recovering rare-earth ions from weathered crust illuviation-type rare-earth ore leaching solution |
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| CN102380102A (en) * | 2011-11-02 | 2012-03-21 | 东华大学 | Method for preparing environment-responsive mesoporous silicon nanoparticles |
| CN104046805A (en) * | 2014-06-27 | 2014-09-17 | 武汉工程大学 | Method for recovering rare-earth ions from weathered crust illuviation-type rare-earth ore leaching solution |
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