CN109926028A - A kind of thiocarbamide trace resin and preparation method thereof and the application in ADSORPTION OF GOLD - Google Patents
A kind of thiocarbamide trace resin and preparation method thereof and the application in ADSORPTION OF GOLD Download PDFInfo
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Abstract
The present invention provides a kind of thiocarbamide trace resin and preparation method thereof and the application in ADSORPTION OF GOLD, the following steps are included: step 1, chitosan is added in gold ion solution, and glacial acetic acid is added, solution A is obtained, stirring forms gel, and gel is processed into gel particle with sodium hydroxide solution, washing, obtains chitosan gel rubber particle；Thiocarbamide and glutaraldehyde are added to the water, are stirred to react to obtain solution B；Step 2, chitosan gel rubber particle is added in solution B, stirring carries out cross-linking reaction, uses elution after products therefrom washing, is washed out, dries, obtain thiocarbamide trace resin.Thiocarbamide trace resin is to the large amount of adsorption of Au, and thiocarbamide trace resin is recyclable, environmentally protective.
Description
Technical field
The invention belongs to golden tailings pollutions to repair field, and in particular to a kind of thiocarbamide trace resin and preparation method thereof and
Extract the application in recycling gold.
Background technique
Gold plays extremely important effect, especially technology as a kind of rare precious metal in social and economic activities
The equipment of upper high, precision and frontier, it is huge using the number of components of gold.
The production of gold mainly includes being crushed/fine grinding, ore dressing, pretreatment, leaching, extraction and recycling, the processes list such as refining
Member.Though using the non-cyanidation golds method such as cyanidation gold-extracted method or chloridising, Thiourea-uv Method, thiosulfate technique, gold mine warp
It crosses after leaching process, gold is final all with AuCl4 -The form of equal complexs and other accompanying elements coexist in leachate.It passes through again
Crossing extraction removal process can be obtained thick gold, therefore Au plasma and recycling are one very heavy in golden production process in leachate
The link wanted, Au plasma efficiency are directly related to the efficiency of entire production process.
Meanwhile gold can usually generate the golden waste liquid of a large amount of leaching in extracting removal process, gold is much more stable with property
AuCl4 -Complex anion form exists in solution.Waste liquid still contains micro or Determination of trace gold after preliminary treatment, though golden concentration
Low, waste liquid amount is but very huge, if direct emission, it will is lost the more considerable gold of quantity, not only causes the very big wave of resource
Take, while also quite serious to the pollution of environment, especially the pollution of water resource can not be ignored.In view of environmentally friendly and economy
Double benefit, Au plasma recycling seems especially urgent and significant in waste liquid.
The method for extracting recycling gold has very much, and wherein zinc displacement method, electrodeposition method, solvent extraction, absorption method etc. are the most
Common gold extracting method.Absorption method is the gold extracting method being most widely used at present, have it is high-efficient, equipment and it is easy to operate,
Many advantages, such as adsorbent is renewable and Reusability, low in the pollution of the environment, is increasingly taken seriously in the separation of noble metal.Often
The active charcoal of adsorbent and ion exchange resin, gold desorb after being adsorbed on adsorbent by method appropriate
Achieve the purpose that recycling gold.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of thiocarbamide trace resin and preparation method thereof and is inhaling
Application in attached gold, to the large amount of adsorption of Au, and thiocarbamide trace resin is recyclable, environmentally protective.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of thiocarbamide trace resin, comprising the following steps:
Step 1, chitosan is added in gold ion solution, and glacial acetic acid is added, obtain solution A, stirring forms gel, coagulates
Glue is processed into gel particle with sodium hydroxide solution, and washing obtains chitosan gel rubber particle；Water is added in thiocarbamide and glutaraldehyde
In, it is stirred to react to obtain solution B；
Step 2, chitosan gel rubber particle is added in solution B, stirring carries out cross-linking reaction, uses after products therefrom washing
Elution is washed out, and drying obtains thiocarbamide trace resin.
Preferably, in step 1, chitosan, gold ion, glutaraldehyde and thiocarbamide amount ratio are as follows: 1g:(0.055-0.277)
Mmol:(4-9) mL:(0.5-3) g.
Preferably, in step 1, the mass fraction of glacial acetic acid is 1%-3% in solution A.
Preferably, in step 1, solution A stirs at 50 DEG C and forms gel, and thiocarbamide and glutaraldehyde are stirred to react at 50 DEG C
Obtain solution B.
Preferably, in step 2, cross-linking reaction temperature is 70 DEG C, and the time is 2~8h.
Preferably, in step 2, elution is specifically: eluent is the mixed solution of thiocarbamide and sulfuric acid.
The thiocarbamide trace resin being prepared using the preparation method.
Application of the thiocarbamide trace resin in ADSORPTION OF GOLD.
Preferably, comprising the following steps:
(1) thiocarbamide trace resin, oscillation, using in thiocarbamide trace resin adsorption solution are added into the solution containing gold ion
Gold ion；
(2) it is centrifugated or filters after adsorbing.
Preferably, in step (1), pH value of solution range of the adjusting containing gold ion is 1-7, then is adsorbed.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention uses thiocarbamide for function monomer, glutaraldehyde as cross linker, and chitosan is substrate, and Au is object ion, leads to
Cross imprinted crosslinked synthesizing thiourea trace resin.Chitosan contains a large amount of amino group (- NH2) or hydroxyl group (- OH), make to live
Property functional group introduce be easier, by acylations, carboxylated etc. reaction will contain the active group of the elements such as N, O, S introduce divides
In subchain, increase adsorption site density.Sulfydryl is to highly polar metal ion (such as Hg2+, Ag+And Au3+Deng) there is special complexing
Ability can form stable chelation structure.Its adsorption capacity and selectivity can be improved through thiocarbamide modification in chitosan, it may be assumed that thiocarbamide
Play modification, it is possible to increase the adsorbance of product.The key property of thiocarbamide is to generate surely with transition metal ion in aqueous solution
Fixed complex cation.The richer N and S that thiocarbamide contains compared with the polyethyleneimine that existing trace resin uses, makes to adsorb
Site density increases, and adsorbance improves.It is imprinted crosslinked, on the one hand in the sky of Au-TUCS surface formation energy specific recognition Au (III)
Cave structure has reserved the functional group that can effectively combine Au (III) in these void structures, has specific recognition ability to Au (III)
Energy；On the other hand, after crosslinking, amino content on resin is caused to have although the amino of chitosan is reacted with the aldehyde radical of glutaraldehyde
Declined, but a degree of weakening occurs for its crystalline texture, weakens the hydrogen bond action on its strand between amino and hydroxyl,
Cause its adsorption site activity is opposite to increase, it is easier to which, in conjunction with Au (III), the thiocarbamide trace resin adsorption capacity obtained from is big.
Crosslinking agent forms imprinted cavity to resin and plays an important role, it is conducive to fixed trace Au (III), and being formed has trace empty
The rigid polymer of cave structure can react since the both ends of glutaraldehyde molecules chain have aldehyde radical with the amino of chitosan, chain
The strand of Sales glycan, the webbed polymer of shape are connect, therefore selecting glutaraldehyde is ideal crosslinking agent.The sulphur that the present invention synthesizes
Urea trace resin, compared with conventional adsorbent, thiocarbamide trace resin is easy to separate with solution, can be to thiocarbamide trace tree after separation
Rouge is eluted, and resin forms imprinted cavity, and imprinted cavity adsorbs gold ion after elution, can be reused.
Further, glutaraldehyde and gold ion dosage are controlled, the quantity of imprinted cavity can be controlled, is held to adjust absorption
Amount.
Further, by controlling crosslinking time, the imprinted cavity quantity of formation can be controlled, is held to adjust absorption
Amount.
The thiocarbamide trace resin that the present invention synthesizes, adsorption capacity is big, is easy to separate with solution, can print to thiocarbamide after separation
Mark resin is eluted, and can be reused after elution.
Thiocarbamide trace resin of the invention can be applied to ADSORPTION OF GOLD, by controlling acid-base property condition, adjustable adsorbance.
Detailed description of the invention
To the adsorption isotherm of Au (III) ion, abscissa is in supernatant for Figure 1A u-TUCS resin and NI-TUCS resin
The concentration of gold ion is remained, ordinate is the gold ion amount adsorbed in resin；
Fig. 2 is influence of the different glutaraldehyde dosages to thiocarbamide trace resin adsorption performance；
Fig. 3 is influence of the different crosslinking times to thiocarbamide trace resin adsorption performance；
Fig. 4 is influence of the different gold ion dosages to thiocarbamide trace resin adsorption performance；
Fig. 5 pH is to the influence to thiocarbamide trace resin adsorption performance.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The preparation process of thiocarbamide trace resin of the present invention, comprising the following steps:
Step 1, a certain amount of chitosan is taken, certain density gold ion solution stirring is added, glacial acetic acid is added, obtains solution
A stirs a period of time at 50 DEG C, is formed after gel and is processed into gel particle with 0.5M sodium hydroxide solution, washing removal is extra
Gold ion, wash to neutrality, obtain chitosan gel rubber particle.The mass fraction of glacial acetic acid is 2% in solution A.
Step 2, in four-hole boiling flask, a certain amount of water, thiocarbamide, glutaraldehyde is added, stirs a period of time at 50 DEG C.By shell
Polysaccharide gel particle is added in above-mentioned four-hole boiling flask, and stirring carries out cross-linking reaction at 70 DEG C, stops stirring, is allowed to cool to room
Temperature, products therefrom dehydrated alcohol, distillation water washing, is vibrated at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution)
10h, elution wash until gold ion elutes completely on product when being detected with 1M sodium sulfide solution to neutrality, at 50 DEG C
Lower drying obtains thiocarbamide trace resin (Au-TUCS).
Wherein, the amount ratio of chitosan, gold ion and glutaraldehyde are as follows: 1g:(0.055-0.277) mmol:(4-9) mL.Gold
The concentration of trace ion A u is 200~1000mg/L in solion.Gold ion solution chlorauric acid solution.
In step 2, crosslinking time is 2~8h.
Utilize the method for Au in thiocarbamide trace resin adsorption solution, comprising the following steps:
(1) thiocarbamide trace resin is added into the solution containing gold ion, then vibrates 4h at 28 DEG C, utilizes thiocarbamide trace
Resin adsorption GOLD FROM PLATING SOLUTION ion.The ratio of thiocarbamide trace resin and Au solution is (0.01~0.03g): 20mL.
(2) it is centrifugated or filters after adsorbing, obtain the thiocarbamide trace resin of ADSORPTION OF GOLD；
(3) by after the thiocarbamide trace resin elution after absorption, washing to neutrality, drying is re-used for adsorbing
Gold in solution.
Below with reference to embodiment, the invention will be described in further detail:
Embodiment 1: the comparison of Au in thiocarbamide trace resin and non-trace resin adsorption solution, and with thiocarbamide trace resin
With the comparison of Au in other trace resin adsorption solution
Prepare thiocarbamide trace resin:
1g chitosan is weighed, addition 50mL concentration is 600mLL-1In chlorauric acid solution, stirring adds glacial acetic acid, makes
Glacial acetic acid mass concentration is 2%, and 4h is stirred at 50 DEG C, is formed after gel and uses 0.5M sodium hydroxide, washing remove extra gold from
Son, washing to neutrality.
In four-hole boiling flask, a certain amount of water is added, weighs 0.5g thiocarbamide, 50% glutaraldehyde of 15mL stirs at 50 DEG C
4h.Four-hole boiling flask is added in the gel particle of chitosan, 6h is stirred at 70 DEG C, stops stirring, is allowed to cool to room temperature nothing
Resin is vibrated 10h with eluent (0.5M thiocarbamide+1M sulfuric acid solution), use is above-mentioned by water-ethanol, distilled water, washing at 28 DEG C
Elution, until show that gold ion elutes completely on thiocarbamide trace resin with the detection of 1M sodium sulfide solution, washing to neutrality.
It is dried at 50 DEG C.
Prepare non-trace resin (NI-TUCS):
It weighs 1g chitosan and 50mL deionized water stirring addition glacial acetic acid (2%) is added, 4h is stirred at 50 DEG C, forms gel
It is washed afterwards with 0.5M sodium hydroxide solution to neutrality.
In four-hole boiling flask, 50mL deionized water is added, weighs the thiocarbamide of 0.5g, 50% glutaraldehyde of 15mL stirs at 50 DEG C
Mix 4h.Four-hole boiling flask is added in the gel particle of chitosan, 6h is stirred at 70 DEG C, stops stirring, is allowed to cool to room temperature use
Dehydrated alcohol, distilled water, washing are dried at 50 DEG C.
The thiocarbamide trace resin and the gold ion in non-trace resin adsorption chlorauric acid solution that preparation is respectively adopted, filtering,
Supernatant is taken, its gold content is surveyed using Flame Atomic Absorption Spectrometry.
It is detected through Flame Atomic Absorption Spectrometry, the result is shown in Figure 1, it can be seen that thiocarbamide trace resin is to the golden adsorbance in solution
It is doubled compared to non-trace resin.Trace has apparent advantage compared with non-trace, this is because after imprinted crosslinked, in Au-
The void structure of TUCS surface formation energy specific recognition Au (III) has been reserved and can effectively combine Au's (III) in these void structures
Functional group has singleness identity to Au (III)；On the other hand, after crosslinking, although leading to amino content on resin
Declined, but a degree of weakening occurs for its crystalline texture, subtracts the hydrogen bond action on its strand between amino and hydroxyl
It is weak, cause its adsorption site activity is opposite to increase, it is easier in conjunction with Au (III).
Embodiment 2: influence of the various concentration acetic acid solution to thiocarbamide trace resin adsorption performance
Preparation process:
2g thiocarbamide being added in four-hole bottle, 50mL deionized water is added, the volume that 50% glutaraldehyde is added is respectively 15mL, and 50
At DEG C, 4h is reacted.
It is 600mLL that 50mL concentration, which is added, in 1g chitosan-1Chlorauric acid solution in, stirring, be added glacial acetic acid, make ice second
Sour mass concentration is respectively 1%, 2%, 3% to carry out three groups of experiments in parallel, and at 50 DEG C, trace 4h is 0.5mol/L's with concentration
Naoh treatment is washed with deionized at gel particle to neutrality.
Chitosan gel rubber particle is added in above-mentioned four-hole bottle, at 70 DEG C, stirs 6h, with dehydrated alcohol, deionization washing
It washs, resin is vibrated into 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution), with above-mentioned elution, until using
The detection of 1M sodium sulfide solution shows that gold ion elutes completely on thiocarbamide trace resin, washing to neutrality.It is dried at 50 DEG C.
The thiocarbamide trace resin of 0.01g is added into the solution of Au containing 20mL, then utilizes thiocarbamide trace resin adsorption solution
The method of middle Au vibrates 4h at 28 DEG C, and filtering takes supernatant, surveys its gold content using Flame Atomic Absorption Spectrometry.
With Flame Atomic Absorption Spectrometry test sample, the results show that when chitosan acetic acid concentration is 1%, slow curing, gel particle balling-up
Property is bad；When chitosan acetic acid concentration is 2%, quick solidifying, gel particle is round and smooth, loose, is conducive to adsorb；Chitosan acetic acid is dense
When degree is 3%, quick solidifying, gel particle is solid, fine and close.Wherein, when acetic acid concentration is 2%, the adsorbance of resin is up to
4.82mmol·L-1, therefore, the concentration for the best acetic acid solution that the present invention selects is 2%.
Embodiment 3: influence of the different glutaraldehyde dosages to thiocarbamide trace resin adsorption performance
Crosslinking agent forms imprinted cavity to resin and plays an important role, it is conducive to fixed trace Au (III), forms tool
There is the rigid polymer of imprinted cavity structure.Since the both ends of glutaraldehyde molecules chain have acidic group, can be sent out with the amino of chitosan
Raw reaction, links the strand of Sales glycan, the webbed polymer of shape.Therefore selection glutaraldehyde is ideal crosslinking agent.
Preparation process:
3g thiocarbamide is added in four-hole bottle, 50mL deionized water is added, the volume that 50% glutaraldehyde is added is respectively 8,10,12,
14,16,18mL carries out parallel laboratory test, at 50 DEG C, reacts 4h.
It is 600mLL that 50mL concentration, which is added, in 1g chitosan-1Chlorauric acid solution in, stirring, be added 1mL glacial acetic acid, make
Glacial acetic acid mass concentration is 2%, at 50 DEG C, trace 4h, and the naoh treatment for being 0.5mol/L with concentration is used at gel particle
Deionized water is washed to neutrality.
Chitosan gel rubber particle is added in above-mentioned four-hole bottle, at 70 DEG C, stirs 6h, with dehydrated alcohol, deionization washing
It washs, resin is vibrated into 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution), with above-mentioned elution, until using
The detection of 1M sodium sulfide solution shows that gold ion elutes completely on thiocarbamide trace resin, washing to neutrality.It is dried at 50 DEG C.
The thiocarbamide trace resin of 0.01g is added into the solution of Au containing 20mL, then utilizes thiocarbamide trace resin adsorption solution
The method of middle Au vibrates 4h at 28 DEG C, and filtering takes supernatant, surveys its gold content using Flame Atomic Absorption Spectrometry.
With Flame Atomic Absorption Spectrometry test sample, as a result as shown in fig. 2, it can be seen that the increase of the dosage with glutaraldehyde, makes shape
At imprinted cavity increase, adsorption capacity increase.Then reducing again is due to the increase with glutaraldehyde, and imprinted cavity reaches most
Greatly, effective adsorption site is reduced in thiocarbamide trace resin, reduces its adsorption capacity.Therefore, it in the case where 1g chitosan, closes
It is 12mL at optimal 50% glutaraldehyde dosage in the process.
Embodiment 4: influence of the different crosslinking times to thiocarbamide trace resin adsorption performance
3g thiocarbamide is added in four-hole bottle, 50mL deionized water is added, be added 50% glutaraldehyde 12mL, at 50 DEG C, reacts 4h.
It is 600mLL that 50mL concentration, which is added, in 1g chitosan-1Chlorauric acid solution in, stirring, be added 1mL glacial acetic acid, make
Glacial acetic acid mass concentration is 2%, at 50 DEG C, trace 4h, and the naoh treatment for being 0.5mol/L with concentration is used at gel particle
Deionized water is washed to neutrality.
Chitosan gel rubber particle is added in four-hole bottle, at 70 DEG C, mixing time is respectively 2,3,4,5,6,7h, and use is anhydrous
Ethyl alcohol, deionized water washing, vibrates 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution) for resin, is washed with above-mentioned
De- liquid elution, until show that gold ion elutes completely on thiocarbamide trace resin with the detection of 1M sodium sulfide solution, washing to neutrality.?
It is dried at 50 DEG C.
The thiocarbamide trace resin of 0.01g is added into the solution of Au containing 20mL, then utilizes thiocarbamide trace resin adsorption solution
The method of middle Au vibrates 4h at 28 DEG C, takes supernatant, surveys its gold content using Flame Atomic Absorption Spectrometry.
With Flame Atomic Absorption Spectrometry test sample, as a result as shown in figure 3, it can be seen from the figure that with crosslinking time before 5h
Increase, the amino of chitosan reacts more abundant with the aldehyde radical of glutaraldehyde, and the imprinted cavity of formation increases, and increases adsorbance, 5h
It is full cross-linked, it forms trace amount and reaches maximum, continue to be crosslinked most amino and crosslinking agent association reaction later, lose combination
The ability of Au (III), therefore amino content is declined on resin, then adsorption capacity is declined, then best crosslinking time 5h.
Embodiment 5: influence of the different gold ion dosages to thiocarbamide trace resin adsorption performance
3g thiocarbamide is added in four-hole bottle, 50mL deionized water is added, be added 50% glutaraldehyde 12mL, at 50 DEG C, reacts 4h.
1g chitosan is added in chlorauric acid solution of the 50mL containing various concentration, chlorauric acid solution concentration is respectively 218.6,
437.2,1mL glacial acetic acid is added in 546.5,655.8,874.4,1093mg/L, stirring, make glacial acetic acid mass concentration 2%, 50
At DEG C, trace 4h, the naoh treatment for being 0.5mol/L with concentration is washed with deionized at gel particle to neutrality.
Chitosan gel rubber particle is added in four-hole bottle, at 70 DEG C, mixing time 6h, with dehydrated alcohol, deionization washing
It washs, resin is vibrated into 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution), with above-mentioned elution, until using
The detection of 1M sodium sulfide solution shows that gold ion elutes completely on thiocarbamide trace resin, washs to neutrality, dries at 50 DEG C.
The thiocarbamide trace resin of 0.01g is added into the solution of Au containing 20mL, then utilizes thiocarbamide trace resin adsorption solution
The method of middle Au vibrates 4h at 28 DEG C, takes supernatant, surveys its gold content using Flame Atomic Absorption Spectrometry.
Through Flame Atomic Absorption Spectrometry test sample, as a result as shown in figure 4, it can be seen from the figure that the increase of the concentration of Au (III), sulphur
The adsorption capacity of urea trace resin is gradually increased.Illustrate the increase of the quantity of trace Au (III) so that being formed on thiocarbamide trace resin
Imprinted cavity quantity increase, to improve the selective adsorption capacity to Au (III).When Au (III) concentration is less than 655mg/L
When, the amino of chitosan is not combined with Au (III) all, and as Au (III) concentration increases, the imprinted cavity of formation also increases,
Adsorbance increases, then after crosslinking, when Au (III) concentration is greater than 655mg/L, adsorption capacity decreases.
Embodiment 6: optimum condition synthesis
It is 650mLL that 50mL concentration, which is added, in 1g chitosan-1Chlorauric acid solution in, stirring, be added 1mL glacial acetic acid, make ice
Quality of acetic acid concentration is 2%, and 4h is stirred at 50 DEG C, is formed after gel and is processed into gel particle with 0.5M sodium hydroxide (150mL),
Washing removes extra gold ion, washing to neutrality.
In four-hole boiling flask, 50mL water, 3g thiocarbamide is added, 50% glutaraldehyde of 12mL stirs 3h at 50 DEG C.By chitosan
Above-mentioned four-hole boiling flask is added in gel particle, and 5h is stirred at 70 DEG C, stops stirring, is allowed to cool to room temperature dehydrated alcohol, steams
Distilled water, washing, vibrates 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution) for resin, is washed with above-mentioned eluent
It is de-, until show that gold ion elutes completely on thiocarbamide trace resin with the detection of 1M sodium sulfide solution, washing to neutrality.At 50 DEG C
Drying.
Influence of the embodiment 7:pH to thiocarbamide trace resin adsorption performance
Taking 20mL concentration is the chlorauric acid solution of 350mg/l, is respectively with 2M sodium hydroxide or 1M hydrochloric acid conditioning solution pH
1,2,3,4,5,6,7, the thiocarbamide trace resin for being separately added into 10mg synthesis vibrates 4h at 28 DEG C, filters, is inhaled with NITRATE BY FLAME ATOMIC
Receive the concentration of gold ion in detection filtrate.
It is non-trace resin by thiocarbamide trace resin replacement, carries out check experiment with same method.
As a result as shown in figure 5, as seen from the figure, suction of the thiocarbamide trace resin than non-trace resin under condition of different pH
Attached amount is high, and with the increase of pH, and the adsorbance of thiocarbamide trace resin and non-trace resin is declined, therefore the thiocarbamide prints
Mark resin has preferable adsorption effect to the Au in solution in acid condition.
Embodiment 8: thiocarbamide trace resin recycles
Taking 20mL concentration is the chlorauric acid solution of 350mg/l, and the thiocarbamide trace resin that 10mg synthesis is added shakes at 28 DEG C
4h is swung, filters, the resin after absorption is vibrated into 10h at 28 DEG C with eluent (0.5M thiocarbamide+1M sulfuric acid solution), is washed with above-mentioned
De- liquid elution, until show that gold ion elutes completely on thiocarbamide trace resin with the detection of 1M sodium sulfide solution, washing to neutrality.?
It is dried at 50 DEG C.Taking 20mL concentration is the chlorauric acid solution of 350mg/l, and the thiocarbamide trace resin of 10mg elution is added at 28 DEG C
Vibrate 4h, filtering, with the concentration of gold ion in Flame Atomic Absorption Spectrometry detection filtrate.Au-TUCS is to Au Cl4 –Adsorbance it is basic
It remains unchanged, 3.19mg/g when being only down to the 2nd time from the 3.27 of the 1st time, the range of decrease is only 2.45%, this absolutely proves thiocarbamide
Trace resin has excellent repeat performance.
Compared with trace resin in the prior art, 1 the results are shown in Table, it can be seen that the absorption of thiocarbamide trace resin of the present invention
Amount is significantly improved compared with prior art.
Absorption situation of the different adsorbents of table 1 to Au (III)
[1]Monier M,Akl M A,Ali W.Preparation and characterization of
selective phenyl thiosemicarbazide modified Au(III)ion-imprinted cellulosic
cotton fibers[J].Journal of Applied Polymer Science,2014,131(18):9277-9287.
[2] An Fuqiang, Yue Xiaoxia, Guo Xudong wait the aminated modified D301 resin of to Au Cl4 –Absorption and recognition performance
[J] functional material, 2016,47 (9): 9 220-9 225.
[3] Yue Xiaoxia, Zhang Dong, Du Ruikui wait Silica Surface Au Cl4 –The preparation of trace polyethyleneimine and evident characteristics
Study [J] noble metal, 2015,36 (2): 1-8.
Claims (10)
1. a kind of preparation method of thiocarbamide trace resin, which comprises the following steps:
Step 1, chitosan is added in gold ion solution, and glacial acetic acid is added, obtain solution A, stirring forms gel, and gel is used
Sodium hydroxide solution is processed into gel particle, and washing obtains chitosan gel rubber particle；Thiocarbamide and glutaraldehyde are added to the water, stirred
It mixes reaction and obtains solution B；
Step 2, chitosan gel rubber particle is added in solution B, stirring carries out cross-linking reaction, with elution after products therefrom washing
Liquid elution, is washed out, and dries, obtains thiocarbamide trace resin.
2. the preparation method of thiocarbamide trace resin according to claim 1, which is characterized in that in step 1, chitosan, gold
The amount ratio of ion, glutaraldehyde and thiocarbamide are as follows: 1g:(0.055-0.277) mmol:(4-9) mL:(0.5-3) g.
3. the preparation method of thiocarbamide trace resin according to claim 1, which is characterized in that in step 1, ice in solution A
The mass fraction of acetic acid is 1%-3%.
4. the preparation method of thiocarbamide trace resin according to claim 1, which is characterized in that in step 1, solution A is 50
Stirring forms gel, thiocarbamide and glutaraldehyde and is stirred to react to obtain solution B at 50 DEG C at DEG C.
5. the preparation method of thiocarbamide trace resin according to claim 1, which is characterized in that in step 2, cross-linking reaction temperature
Degree is 70 DEG C, and the time is 2~8h.
6. the preparation method of thiocarbamide trace resin according to claim 1, which is characterized in that in step 2, elution is specific
Be: eluent is the mixed solution of thiocarbamide and sulfuric acid.
7. the thiocarbamide trace resin being prepared using preparation method described in any one of claims 1-6.
8. application of the thiocarbamide trace resin as claimed in claim 7 in ADSORPTION OF GOLD.
9. application according to claim 8, which comprises the following steps:
(1) into the solution containing gold ion be added thiocarbamide trace resin, oscillation, using thiocarbamide trace resin adsorption GOLD FROM PLATING SOLUTION from
Son；
(2) it is centrifugated or filters after adsorbing.
10. application according to claim 8, which is characterized in that in step (1), adjust the pH value of solution range containing gold ion
For 1-7, then adsorbed.
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