CN103894158A - Preparation method and application of palladium adsorption material - Google Patents
Preparation method and application of palladium adsorption material Download PDFInfo
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- CN103894158A CN103894158A CN201410124253.XA CN201410124253A CN103894158A CN 103894158 A CN103894158 A CN 103894158A CN 201410124253 A CN201410124253 A CN 201410124253A CN 103894158 A CN103894158 A CN 103894158A
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Abstract
The invention discloses a preparation method and application of a palladium adsorption material. The preparation method comprises the following steps: blending chitosan and montmorillonite, adding glutaraldehyde to serve as a cross-linking agent, and preparing a chitosan-montmorillonite cross-linking blended film. The defects that the chitosan is poor in mechanical performance and low in acid resistance can be overcome, the cross-linking blended film serves as a palladium adsorption material, and precious metal palladium can be effectively adsorbed and separated. The palladium adsorption material prepared by the method provided by the invention is in a film structure, serves as solid-phase packing to prepare an adsorption column and has the advantages of improving mass transfer resistance and promoting elution.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of palladium sorbing material.
Background technology
Metal Palladium (Pd) is the metal of earth reserves rareness, is widely used in preparation industry and auto-exhaust catalyst.In product from using, reclaim palladium and have important economic implications, current recovery method is mainly liquid-liquid extraction and the precipitation method, in liquid-liquid extraction, in a large number with an organic solvent, easily causes secondary pollution; The precipitation method easily cause the loss of noble metal.Solid phase extraction techniques, because of its extraction process simple and quick (general analysis only needs 5～20 min), is 1/10 of liquid-liquid extraction method; Solvent is economized, and only needs 10% of liquid-liquid extraction method; Favorable reproducibility and the rate of recovery are high, and have reduced the introducing of impurity, easily realize automation.These advantages make solid phase extraction techniques have good development prospect, are more and more applied in metal enrichment and reclaim.Solid phase extraction filler mostly is fine particle thing at present, as silica gel, active carbon, fluoropolymer resin class.The present invention develops a kind of membrane material, can adopt higher flow, further shortens the time of enriching and recovering and reduces its resistance to mass tranfer.
Shitosan is the natural polymer chain polysaccharide with amino and hydroxyl, and well adsorbing metal ions, has the good advantage such as film forming and Biodegradable.Shitosan is as the biodegradable biomaterial of one, and reserves are huge, if use it in the recovery of precious metal palladium, both can be in order to avoid the pollution of a large amount of organic solvents that liquid-liquid extraction brings, more can reduce the cost of raw material that reclaims palladium.Montmorillonite is a kind of natural minerals, and the ion-exchange capacity that it is good makes it containing being used widely in heavy metal water treatment field.At present, mostly shitosan and montmorillonite blend are formed to resin microsphere shape, for recycling heavy metal, have no shitosan and montmorillonite are prepared into film material for reclaiming the report of noble metal.
Summary of the invention
The object of the invention is to overcome the difficult point of prior art, a kind of preparation method and application thereof of palladium sorbing material are provided.
The technical solution used in the present invention is:
A preparation method for palladium sorbing material, comprises the following steps:
(1) shitosan is dissolved in acetic acid, obtains solution A; Montmorillonite is scattered in acetic acid, obtains solution B;
(2) under stirring, solution B is added to solution A, be warming up to 40～60 ℃, stirring reaction, obtains solution C; In solution C, the mass ratio of shitosan and montmorillonite is 10～20:1;
(3) then under stirring, add appropriate glutaraldehyde to solution C, continue stirring reaction, obtain casting solution;
(4) casting solution is coated on supporter, dries, obtain membrane material;
(5) membrane material is joined in coagulating bath, solidify, obtain palladium sorbing material.
Preferably, the mass ratio of shitosan and glutaraldehyde is 1000:(1～10), preferred, be 1000:(5～6).
Preferably, step (2), stirring reaction 1～2h.
Preferably, step (3), stirring reaction 2～4h.
Preferably, step (4) is dried under 40～80 ℃ of conditions.
Preferably, step (5), the mixed liquor of the NaOH solution that coagulating bath is 1～6wt% or itself and absolute ethyl alcohol.
Preferably, step (5), solidifies 1～4h.
Preferably, step (5), the thickness of palladium sorbing material is 0.5～1.0mm.
Preferably, step (1), acetate concentration is 1～3v/v%.
Preferably, glutaraldehyde is mixed with after the aqueous solution of 1～5wt%, adds solution C.
Preferably, solution B is added after solution A, reaction temperature control is 40～60 ℃, make shitosan better intercalation between montmorillonite layer, and prevent excess Temperature cause shitosan decompose.
The application of above-mentioned palladium sorbing material in enrichment, recovery Metal Palladium.
The invention has the beneficial effects as follows:
The present invention is by shitosan and montmorillonite blend, add glutaraldehyde as crosslinking agent, prepare the crosslinked blend film of shitosan-montmorillonite, overcome the shortcomings such as chitosan film bad mechanical property, acid-resisting be poor, this crosslinked blend film is as palladium sorbing material, effectively adsorbing separation precious metal palladium.
Palladium sorbing material prepared by the present invention is film like structures, prepares adsorption column as solid phase filler, has the resistance to mass tranfer of improvement, is easy to the advantages such as wash-out.
Accompanying drawing explanation
Fig. 1 is absorption Pd
2+the Electronic Speculum figure of the front crosslinked blend film of shitosan-montmorillonite;
Fig. 2 is absorption Pd
2+after the Electronic Speculum figure of the crosslinked blend film of shitosan-montmorillonite;
Fig. 3 is the XRD collection of illustrative plates of montmorillonite and chitosan film;
Fig. 4 is the XRD collection of illustrative plates of montmorillonite-chitosan mixed film, the crosslinked blend film of shitosan-montmorillonite;
Fig. 5 is different Pd
2+under the condition of initial concentration, the adsorption effect of three kinds of membrane materials.
The specific embodiment
Below in conjunction with specific embodiment, further set forth content of the present invention.
embodiment 1
The preparation method of palladium sorbing material (shitosan-montmorillonite is cross-linked blend film), comprises the following steps:
(1) 1g shitosan is dissolved in the acetic acid of 40ml 2v/v%, is stirred to formation clear solution, obtain solution A; 0.1g montmorillonite is infiltrated with 10ml 2v/v% acetic acid, and ultrasonic 2h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 50 ℃, magnetic agitation 2h, obtains solution C;
(3) under stirring, drip the 1wt% glutaraldehyde solution of 0.5ml to solution C, continue after stirring reaction 4h, form yellow casting solution uniformly;
(4) casting solution is coated on supporter, is positioned in 55 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(5) yellow membrane material is immersed in the NaOH solution of 4wt%, solidify 2h, form the thick translucent membrane material of yellow of 0.8mm, i.e. palladium sorbing material, after deionized water rinsing is clean, 4 ℃ of preservations.
embodiment 2
In step (3), the addition of glutaraldehyde is respectively the 1wt% glutaraldehyde water solution of 0.1ml, 0.4ml, 0.5ml, 0.6ml, 0.8ml, 1.0ml, and other steps are with embodiment 1.
Along with the increase of glutaraldehyde consumption, the yellow of step (5) gained palladium sorbing material is deepened gradually, after increasing to 0.6ml, film easy fracture, therefore, consider the physical property of sorbing material and acid-soluble, the mass ratio of shitosan and glutaraldehyde is preferably 1000:(1～10), most preferably be 1000:(5～6).
embodiment 3
The preparation method of palladium sorbing material, comprises the following steps:
(1) 2g shitosan is dissolved in the acetic acid of 100ml 3v/v%, is stirred to formation clear solution, obtain solution A; 0.1g montmorillonite is infiltrated with 10ml 3v/v% acetic acid, and ultrasonic 2h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 40 ℃, magnetic agitation 2h, obtains solution C;
(3) under stirring, drip the 2wt% glutaraldehyde solution of 0.6ml to solution C, continue after stirring reaction 3h, form yellow casting solution uniformly;
(4) casting solution is coated on supporter, is positioned in 80 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(5) yellow membrane material is immersed in the NaOH solution of 1wt%, solidify 4h, form the thick translucent membrane material of yellow of 0.5mm, i.e. palladium sorbing material, after deionized water rinsing is clean, 4 ℃ of preservations.
embodiment 4
The preparation method of palladium sorbing material, comprises the following steps:
(1) 15g shitosan is dissolved in the acetic acid of 400ml 3v/v%, is stirred to formation clear solution, obtain solution A; 1g montmorillonite is infiltrated with 100ml 3v/v% acetic acid, and ultrasonic 4h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 60 ℃, magnetic agitation 1h, obtains solution C;
(3) under stirring, drip the 5wt% glutaraldehyde solution of 1.8ml to solution C, continue after stirring reaction 4h, form yellow casting solution uniformly;
(4) casting solution is coated on supporter, is positioned in 60 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(5) yellow membrane material is immersed in the NaOH solution of 6wt%, solidify 2h, form the thick translucent membrane material of yellow of 1.0mm, i.e. palladium sorbing material, after deionized water rinsing is clean, low temperature is preserved.
The preparation method of palladium sorbing material, comprises the following steps:
(1) 1g shitosan is dissolved in the acetic acid of 40ml 1v/v%, is stirred to formation clear solution, obtain solution A; 0.1g montmorillonite is infiltrated with 10ml 1v/v% acetic acid, and ultrasonic 2h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 50 ℃, magnetic agitation 1.5h, obtains solution C;
(3) under stirring, drip the 1wt% glutaraldehyde solution of 0.3ml to solution C, continue after stirring reaction 2h, form yellow casting solution uniformly;
(4) casting solution is coated on supporter, is positioned in 40 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(5) yellow membrane material is immersed in the absolute ethyl alcohol of 1:1 and the mixed liquor of 4wt% NaOH, solidify 1h, form the thick translucent membrane material of yellow of 0.9mm, i.e. palladium sorbing material, after deionized water rinsing is clean, low temperature is preserved.
embodiment 6
The preparation method of palladium sorbing material, comprises the following steps:
(1) 10g shitosan is dissolved in the acetic acid of 300ml 2v/v%, is stirred to formation clear solution, obtain solution A; 1g montmorillonite is infiltrated with 80ml 2v/v% acetic acid, and ultrasonic 4h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 50 ℃, magnetic agitation 2h, obtains solution C;
(3) under stirring, drip the 2wt% glutaraldehyde solution of 2ml to solution C, continue after stirring reaction 3h, form yellow casting solution uniformly;
(4) casting solution is coated on supporter, is positioned in 70 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(5) yellow membrane material is immersed in the absolute ethyl alcohol of 1:2 and the mixed liquor of 4wt% NaOH, solidify 3h, form the thick translucent membrane material of yellow of 0.8mm, i.e. palladium sorbing material, after deionized water rinsing is clean, low temperature is preserved.
comparative example
The preparation of chitosan film:
(1) 1g shitosan is dissolved in the acetic acid of 40ml 2v/v%, is stirred to formation clear solution, obtain casting solution;
(2) casting solution is coated on supporter, is positioned in 55 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(3) yellow membrane material is immersed in the NaOH solution of 4wt%, solidify 2h, obtain the chitosan film that 0.8mm is thick, after deionized water rinsing is clean, 4 ℃ of preservations.
The preparation of shitosan-montmorillonite blend film:
(1) 1g shitosan is dissolved in the acetic acid of 40ml 2v/v%, is stirred to formation clear solution, obtain solution A; 0.1g montmorillonite is infiltrated with 10ml 2v/v% acetic acid, and ultrasonic 2h is dispersed in solution completely to it, obtains solution B;
(2) under stirring, solution B is dropwise joined in solution A, be warming up to 50 ℃, magnetic agitation 2h, obtains casting solution;
(3) casting solution is coated on supporter, is positioned in 55 ℃ of baking ovens and dries, form the yellow membrane material of homogeneous transparent;
(4) yellow membrane material is immersed in the NaOH solution of 4wt%, solidify 2h, obtain shitosan-montmorillonite blend film that 0.8mm is thick, after deionized water rinsing is clean, 4 ℃ of preservations.
performance characterization
(1) by crosslinked shitosan-montmorillonite blend film after liquid nitrogen brittle failure, characterize with ESEM (SEM)
Fig. 1 shows absorption Pd
2+the Electronic Speculum picture of the front crosslinked blend film of shitosan-montmorillonite, Fig. 2 shows absorption Pd
2+after Electronic Speculum picture, the former surperficial smoother, absorption rear surface is coarse shape, proves Pd
2+be adsorbed on each position of film.
(2) XRD(X ray powder diffraction instrument) characterize
Curve in Fig. 3 is respectively the XRD collection of illustrative plates of montmorillonite and chitosan film, in the collection of illustrative plates of montmorillonite, has occurred obvious d in 2 θ=7.13 °
001the diffraction maximum of face, its d
001=1.23.In chitosan film collection of illustrative plates, be 14.15 ° at 2 θ, 16.82 °, 20.02 °, 22.26 ° there is obvious diffraction maximum, consistent with bibliographical information.Fig. 4 demonstration, there is an obvious diffraction maximum, its d in the collection of illustrative plates of montmorillonite-chitosan mixed film (abbreviation blend film) in 2 θ=4.81 °
001=1.83, be increased to 1.83 by 1.23, illustrate shitosan intercalation enter montmorillonite, and enter montmorillonite with double-deck form intercalation, greatly increased homogeney and stability.And adding glutaraldehyde to form after crosslinked blend film, its 2 θ=4.89 °, increase than blend film diffraction maximum, its d
001=1.80, illustrate that adding the montmorillonite impact after intercalation of glutaraldehyde is little, but it is at 10.33 °, 19.91 °, 22.30 ° than the obvious enhancing of blend film, illustrates and has obviously increased order and degree of crystallinity that chitosan molecule is arranged adding of glutaraldehyde, and its physical characteristic is strengthened.
application examples
Take respectively the chitosan film of the 10mg that shitosan-montmorillonite blend film of the 10mg that the crosslinked blend film of shitosan-montmorillonite of the 10mg that 5 parts of embodiment 1 make, 5 parts of comparative examples make, 5 parts of comparative examples make; Immerse respectively in the palladium chloride solution of 20ml containing 0mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L, in 25 ℃ of constant temperature oscillation casees, place after 24h, get supernatant, test Pd by Atomic absorption
2+concentration, calculates adsorbance, and result as shown in Figure 5, visible, different Pd
2+under the condition of initial concentration, the crosslinked blend film of shitosan-montmorillonite has better adsorption effect, works as Pd
2+when initial concentration is 200mg/L, the adsorption capacity of crosslinked blend film is up to 293mg/g.
In adsorption process, the color of the crosslinked blend film of shitosan-montmorillonite is from the pale yellow buff that becomes, and color is very even, illustrates that crosslinked blend film is stable homogeneous.After having adsorbed, the thiourea solution wash-out membrane material of preparation 1g/L, Pd
2+ion desorption enters thiourea solution, reaches the effect of enriching and recovering, regneration of adsorbent material.
Claims (10)
1. a preparation method for palladium sorbing material, comprises the following steps:
(1) shitosan is dissolved in acetic acid, obtains solution A; Montmorillonite is scattered in acetic acid, obtains solution B;
(2) under stirring, solution B is added to solution A, be warming up to 40～60 ℃, stirring reaction, obtains solution C; In solution C, the mass ratio of shitosan and montmorillonite is 10～20:1;
(3) then under stirring, add appropriate glutaraldehyde to solution C, continue stirring reaction, obtain casting solution;
(4) casting solution is coated on supporter, dries, obtain membrane material;
(5) membrane material is joined in coagulating bath, solidify, obtain palladium sorbing material.
2. preparation method according to claim 1, is characterized in that: the mass ratio of shitosan and glutaraldehyde is 1000:(1～10).
3. preparation method according to claim 1, is characterized in that: step (2), stirring reaction 1～2h.
4. preparation method according to claim 1, is characterized in that: step (3), stirring reaction 2～4h.
5. preparation method according to claim 1, is characterized in that: step (4), under 40～80 ℃ of conditions, dry.
6. preparation method according to claim 1, is characterized in that: step (5), the mixed liquor of the NaOH solution that coagulating bath is 1～6wt% or itself and absolute ethyl alcohol.
7. according to the preparation method described in claim 1 or 6, it is characterized in that: step (5), solidify 1～4h.
8. preparation method according to claim 1, is characterized in that: step (5), the thickness of palladium sorbing material is 0.5～1.0mm.
9. preparation method according to claim 1, is characterized in that: step (1), acetate concentration is 1～3v/v%.
10. the application of palladium sorbing material claimed in claim 1 in enrichment, recovery Metal Palladium.
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Cited By (6)
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| CN106345529A (en) * | 2016-07-29 | 2017-01-25 | 绍兴文理学院 | Method for preparing palladium catalytic materials supported by chitosan-modified montmorillonite |
| CN108187503A (en) * | 2018-01-25 | 2018-06-22 | 安徽农业大学 | A kind of preparation method of the enhanced chitosan multiple cellulose acetate film of montmorillonite |
| CN108579693A (en) * | 2018-05-23 | 2018-09-28 | 东华理工大学 | A kind of preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aeroge |
| CN110732311A (en) * | 2019-11-15 | 2020-01-31 | 昆明理工大学 | crosslinked chitosan coated MoS2Adsorbent, preparation method and application thereof |
| CN111167411A (en) * | 2020-01-17 | 2020-05-19 | 长沙凯天工研院环保服务有限公司 | Porous material based on montmorillonite and preparation method and application thereof |
| CN112871138A (en) * | 2019-11-29 | 2021-06-01 | 合肥杰事杰新材料股份有限公司 | Chitosan composite film adsorbent material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345529A (en) * | 2016-07-29 | 2017-01-25 | 绍兴文理学院 | Method for preparing palladium catalytic materials supported by chitosan-modified montmorillonite |
| CN108187503A (en) * | 2018-01-25 | 2018-06-22 | 安徽农业大学 | A kind of preparation method of the enhanced chitosan multiple cellulose acetate film of montmorillonite |
| CN108579693A (en) * | 2018-05-23 | 2018-09-28 | 东华理工大学 | A kind of preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aeroge |
| CN108579693B (en) * | 2018-05-23 | 2021-01-05 | 东华理工大学 | Preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aerogel |
| CN110732311A (en) * | 2019-11-15 | 2020-01-31 | 昆明理工大学 | crosslinked chitosan coated MoS2Adsorbent, preparation method and application thereof |
| CN112871138A (en) * | 2019-11-29 | 2021-06-01 | 合肥杰事杰新材料股份有限公司 | Chitosan composite film adsorbent material and preparation method and application thereof |
| CN111167411A (en) * | 2020-01-17 | 2020-05-19 | 长沙凯天工研院环保服务有限公司 | Porous material based on montmorillonite and preparation method and application thereof |
| CN111167411B (en) * | 2020-01-17 | 2022-12-13 | 长沙凯天工研院环保服务有限公司 | Porous material based on montmorillonite as well as preparation method and application thereof |
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