CN104624159A - 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, relate to a kind of preparation method of nanostructured composite adsorbing material, particularly relate to the application of the rare earth ion in a kind of preparation method of novel maleic acid modified mesoporous silicon material and selective waste suction water.
Background technology
Along with the growth of society's green, low-carbon economy, rare earth element is because its irreplaceable character is at permanent magnet, fluorescent lamp, rechargeable battery, the industrial circles such as catalyst are widely applied, particularly along with hybrid vehicle, wind turbine, a large amount of of compact fluorescent lamp popularize, while the use amount increasing rare earth metal and price, create a large amount of containing the discarded object of a large amount of rare earth element with other metallic elements.These discarded objects are because containing a large amount of rare earth metal and other heavy metal elements, often can not obtain correct process, create the environmental problems such as serious water pollutions and air pollution.
2010, rare earth will be classified as raw material very in short supply by European Union in its important report Critical Raw Materials for the European Union (2010).In the same year, Nd, Eu, Tb, Dy and Y five kinds of rare earth elements will be classified as element the most in short supply in following mid-term by USDOE (DOE) in its annual report.So, the demand of rare earth is within a period of time in future, or can constantly increase, because the rare earth that China is external is rationally supplied with sustainable, the development of low-carbon economy, the prediction world that we can affirm will improve further to rare earth demand very much, and the demand in heavy rare earth element Eu specifically wherein in short supply, Dy future may increase by 700% and 2600% respectively.In the face of the demand of so huge rare earth, as the leading exporter of global rare earth trade, this opportunity being China is also challenge, we are except strengthening rare earth exploitation supervision, rational exploitation, in the face of incident intrinsic rare earth resources reduces rapidly, rare earth resources is as the non-renewable limited resource of preciousness, Recent study personnel are attempting to find new resource to while replacing rare earth, also constantly grinding the recovering rare earth from the solid waste of rare earth that makes internal disorder or usurp, thus enabling rare-earth trade keep sustainable development.Namely reach so-called " equilibrium problem ", namely under any circumstance, the demand and supply of rare earth needs to keep balance, excessively become produce and be recovered as key industry pattern from mining with the Industry Model being separated into emphasis gradually, promote China's Rare-earth Industry sustainable development, make China become rare earth power from rare earth big country.
Mesoporous silicon material because its orderly mesoporous sequence, high specific area (≈ 1000m
2g
-1), high-altitude holds and good biocompatibility and be widely used in chemical industry catalysis, adsorbs, the various aspects such as biology sensor.
The Application and Development of nanostructured composite adsorbing material mesoporous silicon material and high selectivity ligand binding produced is one of research of most attraction.It mainly contains two aspect advantages: the adsorption property utilizing mesoporous silicon material high power capacity on the one hand, improves the adsorption capacity of material.On the other hand, by the grafting of high selectivity part to mesoporous silicon surface, high selectivity part is utilized to improve mesoporous silicon material to the defect of rare earth ion adsorptive selectivity difference to the selectively acting of rare earth ion, prepare the height selection that nanostructured composite adsorbing material meets sorbing material, the demand of high rare earth capacity, becomes the study hotspot in the fields such as current adsorbing separation
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of is that ligand stock carries out the application of the rare earth ion in modification and selective waste suction water to mesoporous silicon material with maleic acid, and this composite modification material has specific adsorption property and higher adsorption capacity to Heavy rare earth.
The present invention realizes above-mentioned technical purpose by following technological means.
To a preparation method for the nanostructured composite adsorbing material of the selective absorption of Heavy rare earth, carry out according to the following steps:
(1) getting softex kw (CTAB) is dissolved in distilled water, keeps mechanical agitation, in solution, drips sodium hydrate aqueous solution; Drip tetraethyl orthosilicate (TEOS), after reaction terminates, filter, washing, calcining, obtains nanometer particle;
(2) nanometer particle ultrasonic disperse step (1) obtained is in toluene solution, then 3-aminopropyl triethoxysilane (APTES) is poured into aaerosol solution, reflux under nitrogen protection 24h, filter, washing, drying, obtains silane-modified nanometer particle;
(3) silane-modified nanometer material step (2) obtained and maleic anhydride (MA), N is scattered in; in N-2-NMF (DMF); add pyridine and form suspension; react under nitrogen protection; solution system becomes rufous, filters, dry; obtain maleic acid modified mesoporous composite material, i.e. nanostructured composite adsorbing material.
Wherein, the concentration after step (1) CTAB is water-soluble is 2.0 ~ 2.1g/L, and the volume ratio of water, TEOS and sodium hydroxide solution is 960:2:7, and 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.
In the final whole mixed solution of step (2) gained, the concentration of nanometer particle is the volume ratio of 12.5 ~ 13.0g/L, APTES and toluene is 2:75.
Washing described in step (1) and step (2) is and washs three times with ethanol.
In step (3), the concentration of modification nanometer material in DMF is 16.5 ~ 17.0g/L; Concentration 23.0 ~ the 23.5g/L of MA, the volume ratio of pyridine and DMF is 1:60.
In step (3), the temperature of reacting under described nitrogen protection is 50 DEG C, and the time is 3h.
Above-mentioned nanostructured composite adsorbing material is applied to the rare earth ion in absorption recovery water sample, and concrete grammar carries out according to following step.
(1) what accurately to take etc. the various rare earth ion of quality is configured to storing solution.
(2) the nanostructured composite adsorbing material getting certain mass adds in the middle of the rare earth ion storing solution of certain volume, as 25 DEG C of absorption 6h in water bath chader.
(3) if initial rare earth ion solubility is C
0, the rare earth ion after absorption is C
t, then nanostructured relapses enclosure material adsorption capacity Q
tcan calculate with equation 1.
W: the quality V of sorbing material: the volume M of rare earth storing solution: the relative atomic mass of rare earth ion
Beneficial effect of the present invention:
(1) adopt high-specific-surface mesoporous material, drastically increase the adsorption capacity of material, and preparation process is simple to operation.
(2) use maleic anhydride as part, compared with the part that other prices are high, significantly reduce the production cost of material.
(3) the nanostructure composite material absorption utilizing the present invention to obtain can be carried out efficiently several Heavy rare earth, high-selectivity adsorption is separated.
Accompanying drawing explanation
Fig. 1: (a) is mesoporous silicon material projection Electronic Speculum figure, (b) is nanostructured composite adsorbing material projection Electronic Speculum figure.
Fig. 2: the FT-IR figure of mesoporous silicon material, nanostructured composite adsorbing material.
Fig. 3: the thermal multigraph of mesoporous silicon material, nanostructured composite adsorbing material.
Fig. 4: mesoporous silicon material, nanostructured composite adsorbing material are to the adsorption experiment figure of rare earth ion.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
(1) 500mgCTAB, is dissolved in 240mL distilled water, keeps mechanical agitation, drips 1.75mL sodium hydroxide solution and 0.5mL TEOS after half an hour.2h is reacted at 80 DEG C, centrifugal, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon materials 1g is dissolved in 75mL toluene.Drip 2mL APTES, reflux one day, obtain silane-modified mesoporous silicon material.
(3) silane-modified for the 0.25g obtained in (2) mesoporous silicon material is scattered in 15mL DMF, then adds 0.35g maleic anhydride (MA), 0.25mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system becomes rufous.Filter, dry, obtain maleic acid modified mesoporous composite material.
(5) mesoporous silicon material, the projection Electronic Speculum figure of nanostructured composite adsorbing material as shown in Figure 1.
(6) mesoporous silicon material, the FT-IR figure of nanostructured composite adsorbing material as shown in Figure 2.In figure 1091 and 3432cm
-1wave number place is respectively as Si-O-Si asymmetric stretching vibration, Si-OH stretching vibration.1650cm
-1and 1550cm
-1wave number place, is CO stretching vibration peak (amine I), NH deformation vibration (amine), shows that part is 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 dehydration, and composite has obvious weightlessness from 150 DEG C, this is because surperficial successful grafting part, modification success is described.
Embodiment 2:
(1) 400mgCTAB, is dissolved in 200mL distilled water, keeps mechanical agitation, drips 1.45mL sodium hydroxide solution and 0.414mL TEOS after half an hour.2h is reacted at 80 DEG C, centrifugal, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon materials 2.06g is dissolved in 160mL toluene.Drip 4.267mL APTES, reflux one day, obtain silane-modified mesoporous silicon material.
(3) silane-modified for the 0.32g obtained in (2) mesoporous silicon material is scattered in 20mL DMF, then adds 0.46g maleic anhydride (MA), 0.333mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system becomes rufous.Filter, dry, obtain maleic acid modified mesoporous composite material.
(5) mesoporous silicon material, the projection Electronic Speculum figure of nanostructured composite adsorbing material as shown in Figure 1.Clearly ordered mesoporous pore canals structure is demonstrated in Fig. 1.
(6) mesoporous silicon material, the FT-IR figure of nanostructured composite adsorbing material as shown in Figure 2.In figure 1091 and 3432cm
-1wave number place is respectively as Si-O-Si asymmetric stretching vibration, Si-OH stretching vibration.1650cm
-1and 1550cm
-1wave number place, is CO stretching vibration peak (amine I), NH deformation vibration (amine II), shows that part is 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, modification success
(8) the nanostructured composite adsorbing material of preparation is used for the separation adsorption experiment of rare earth ion.
Get rare earth ion to be configured to a series of 20mg/L aqueous solution and to be configured to standard reserving solution.Getting 20mg nanostructured composite adsorbing material joins in 10mL colorimetric cylinder, 25
oc concussion evenly, uses ICP-OES to detect residue rare earth ion concentration.
Test result as shown in Figure 4.Wherein dissociation constant K
d,
C
0for rare earth ion initial concentration, C is rare earth ion equilibrium concentration, and V is the volume (mL) of solution, and m is the quality (mg) of adsorbent.
Result shows, nanostructured composite adsorbing material has very high adsorption capacity and very strong selective to Gd ion, and dissociation constant reaches 342, may be used for reclaiming the adsorbing separation of rare earth ion.
Embodiment 3:
(1) 201.6mg CTAB, is dissolved in 96mL distilled water, keeps mechanical agitation, drips 0.7mL sodium hydroxide solution and 0.2mL TEOS after half an hour.2h is reacted at 80 DEG C, centrifugal, wash three times with ethanol.Obtain mesoporous silicon material.
(2) step (1) intermediary hole silicon material 1.3g is dissolved in 100mL toluene.Drip 2.667mL APTES, reflux one day, obtain silane-modified mesoporous silicon material.
(3) silane-modified for the 0.425g obtained in (2) mesoporous silicon material is scattered in 25mL DMF, then adds 0.587g maleic anhydride (MA), 0.417mL pyridine.Under nitrogen protection, 50 DEG C of reaction 3h, solution system becomes rufous.Filter, dry, obtain maleic acid modified mesoporous composite material.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (8)
1. a preparation method for nanostructured composite adsorbing material, is characterized in that, carries out according to following steps:
(1) getting softex kw CTAB is dissolved in distilled water, keeps mechanical agitation, in solution, drips sodium hydrate aqueous solution, drips tetraethyl orthosilicate TEOS, and after reaction terminates, filter, washing, calcining, obtains nanometer particle;
(2) nanometer particle ultrasonic disperse step (1) obtained, in toluene solution, then pours 3-aminopropyl triethoxysilane APTES into aaerosol solution, and reflux under nitrogen protection 24h, filter, washing, dry, obtain silane-modified nanometer particle;
(3) silane-modified nanometer material step (2) obtained and maleic anhydride MA, N is scattered in; in N-2-NMF DMF; add pyridine and form suspension; react under nitrogen protection; solution system becomes rufous, filters, dry; obtain maleic acid modified mesoporous composite material, i.e. nanostructured composite adsorbing material.
2. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, it is characterized in that: in step (1), the concentration after CTAB is water-soluble is 2.0 ~ 2.1g/L, and the concentration of sodium hydroxide solution is 2M; The volume ratio of water, TEOS and sodium hydroxide solution is 960:2:7.
3. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1 and 2, it is characterized in that: 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.
4. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, it is characterized in that, in described step (2), in the final whole mixed solution of gained, the concentration of nanometer particle is the volume ratio of 12.5 ~ 13.0g/L, APTES and toluene is 2:75.
5. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, is characterized in that, washing described in described step (1) and step (2) is and washs three times with ethanol.
6. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, is characterized in that, in described step (3), the concentration of modification nanometer material in DMF is the concentration 23 ~ 23.5g/L of 16.5 ~ 17g/L, MA; The volume ratio of pyridine and DMF is 1:60.
7. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, is characterized in that, in step (3), the temperature of reacting under described nitrogen protection is 50 DEG C, and the time is 3h.
8. the preparation method of a kind of nanostructured composite adsorbing material according to claim 1, is characterized in that, prepared nanostructured composite adsorbing material is applied to and reclaims the adsorbing separation of rare earth ion.
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Cited By (3)
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| CN106000322B (en) * | 2016-06-02 | 2018-10-09 | 江苏大学 | A kind of preparation method of ion blotting and its adsorption applications to dysprosium ion |
| CN109433160A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | A kind of preparation method and application of the hybrid mesoporous silicon adsorbent of double ammonia gantries |
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000322B (en) * | 2016-06-02 | 2018-10-09 | 江苏大学 | A kind of preparation method of ion blotting and its adsorption applications to dysprosium ion |
| CN109433160A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | A kind of preparation method and application of the hybrid mesoporous silicon adsorbent of double ammonia gantries |
| 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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