CN109926028B - Thiourea imprinted resin, preparation method thereof and application thereof in gold adsorption - Google Patents
Thiourea imprinted resin, preparation method thereof and application thereof in gold adsorption Download PDFInfo
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Abstract
The invention provides thiourea imprinted resin, a preparation method thereof and application thereof in gold adsorption, comprising the following steps: step 1, adding chitosan into a gold ion solution, adding glacial acetic acid to obtain a solution A, stirring to form gel, treating the gel into gel particles by using a sodium hydroxide solution, and washing to obtain chitosan gel particles; adding thiourea and glutaraldehyde into water, and stirring for reaction to obtain a solution B; and 2, adding chitosan gel particles into the solution B, stirring for cross-linking reaction, washing the obtained product, eluting with an eluent, washing, and drying to obtain the thiourea imprinted resin. The thiourea imprinted resin has large adsorption capacity to Au, can be recycled and is environment-friendly.
Description
Technical Field
The invention belongs to the field of gold tailing pollution remediation, and particularly relates to thiourea imprinted resin, a preparation method thereof and application thereof in gold extraction and recovery.
Background
Gold is a rare and precious metal, plays an extremely important role in social and economic life, and particularly, the number of parts using gold is huge in technically high, fine and sharp equipment.
Production of goldThe method mainly comprises the process units of crushing/fine grinding, ore dressing, pretreatment, leaching, extraction and recovery, refining and the like. No matter the cyanidation gold extraction method or non-cyanidation gold extraction methods such as chlorination method, thiourea method and thiosulfate method are adopted, gold is finally extracted by AuCl after the gold ore is subjected to the leaching procedure4 -The coordination compound and other accompanying elements coexist in the leaching solution. The coarse gold can be obtained through the extraction and recovery process, so that the extraction and recovery of gold in the leaching solution are very important links in the gold production process, and the extraction efficiency of gold is directly related to the efficiency of the whole production process.
Meanwhile, during the extraction and recovery process of gold, a large amount of gold leaching waste liquid is often generated, and most gold is AuCl with stable property4 -The complex anion form is present in solution. The waste liquid still contains trace or trace gold after the preliminary treatment, although the concentration of gold is low, the waste liquid volume is very huge, if directly discharging, will run off comparatively considerable gold of quantity, not only cause the very big waste of resource, also be very serious to the pollution of environment simultaneously, especially the pollution to the water resource is not neglected. In consideration of the double benefits of environmental protection and economy, the extraction and recovery of gold in the waste liquid are particularly urgent and significant.
There are many methods for extracting and recovering gold, and zinc displacement method, electrodeposition method, solvent extraction method, adsorption method, etc. are the most commonly used methods for extracting gold. The adsorption method is the most widely applied gold extraction method at present, has the advantages of high efficiency, simple equipment and operation, regenerable and reusable adsorbent, less environmental pollution and the like, and is increasingly emphasized in the separation of precious metals. The common adsorbent comprises active carbon and ion exchange resin, and gold is adsorbed on the adsorbent and then desorbed by a proper method, so that the aim of recovering gold can be fulfilled.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the thiourea imprinted resin, the preparation method thereof and the application thereof in gold adsorption, the adsorption amount of Au is large, and the thiourea imprinted resin can be recycled and is environment-friendly.
The invention is realized by the following technical scheme:
a preparation method of thiourea imprinted resin comprises the following steps:
and 2, adding chitosan gel particles into the solution B, stirring for cross-linking reaction, washing the obtained product, eluting with an eluent, washing, and drying to obtain the thiourea imprinted resin.
Preferably, in step 1, the dosage ratio of chitosan, gold ions, glutaraldehyde and thiourea is: 1g (0.055-0.277) mmol: (4-9) mL: (0.5-3) g.
Preferably, in the step 1, the mass fraction of the glacial acetic acid in the solution A is 1-3%.
Preferably, in step 1, the solution A is stirred at 50 ℃ to form a gel, and the thiourea and the glutaraldehyde are stirred and reacted at 50 ℃ to obtain a solution B.
Preferably, in the step 2, the crosslinking reaction temperature is 70 ℃ and the time is 2-8 h.
Preferably, in step 2, the elution is specifically: the eluent is a mixed solution of thiourea and sulfuric acid.
The thiourea imprinted resin is prepared by the preparation method.
The thiourea imprinted resin is applied to gold adsorption.
Preferably, the method comprises the following steps:
(1) adding thiourea imprinted resin into the solution containing the gold ions, oscillating, and adsorbing the gold ions in the solution by using the thiourea imprinted resin;
(2) and after adsorption, centrifugal separation or filtration is carried out.
Preferably, in the step (1), the solution containing gold ions is adjusted to have a pH range of 1-7 and then is adsorbed.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts thiourea asAnd (3) synthesizing the thiourea imprinted resin by imprinting and crosslinking a functional monomer, glutaraldehyde as a crosslinking agent, chitosan as a base material and Au as a target ion. The chitosan contains a large number of amino groups (-NH)2) Or a hydroxyl group (-OH), and introduction of an active functional group is relatively easy, and introduction of an active group containing an element such as N, O, S into a molecular chain by a reaction such as acylation or carboxylation increases the density of adsorption sites. Mercapto group to highly polar metal ion (such as Hg)2+，Ag+And Au3+Etc.) has special complexing ability and can form a stable complex structure. The chitosan is modified by thiourea to improve the adsorption capacity and selectivity, namely: thiourea has the function of modification and can increase the adsorption capacity of the product. An important property of thiourea is the formation of stable complex cations with transition metal ions in aqueous solution. Compared with polyethyleneimine adopted by the existing imprinted resin, thiourea contains more abundant N and S, so that the density of adsorption sites is increased, and the adsorption capacity is improved. On one hand, a cavity structure capable of specifically recognizing Au (III) is formed on the surface of Au-TUCS, functional groups capable of effectively combining Au (III) are reserved in the cavity structures, and the Au-TUCS has specific recognition performance on Au (III); on the other hand, after crosslinking, although the amino group of chitosan reacts with the aldehyde group of glutaraldehyde to reduce the amino group content of the resin, the crystalline structure of the resin is weakened to a certain extent, so that the hydrogen bonding action between the amino group and the hydroxyl group on the molecular chain of the resin is weakened, the activity of the adsorption site of the resin is relatively increased, Au (III) is more easily bonded, and the adsorption capacity of the obtained thiourea imprinted resin is large. The cross-linking agent has an important effect on resin to form imprinting cavities, the cross-linking agent is favorable for fixing imprinting Au (III) and forming a rigid polymer with an imprinting cavity structure, aldehyde groups are arranged at two ends of a glutaraldehyde molecular chain and can react with amino groups of chitosan to link the molecular chain of the chitosan and form a net-shaped polymer, and therefore, glutaraldehyde is selected as an ideal cross-linking agent. Compared with the traditional adsorbent, the thiourea imprinted resin synthesized by the invention is easy to separate from a solution, the thiourea imprinted resin can be eluted after separation, imprinted cavities are formed in the resin, and the imprinted cavities absorb gold ions after elution and can be recycled.
Furthermore, the use amount of glutaraldehyde and gold ions is controlled, the number of imprinted cavities can be controlled, and the adsorption capacity is adjusted accordingly.
Furthermore, the number of formed imprinting cavities can be controlled by controlling the crosslinking time, thereby adjusting the adsorption capacity.
The thiourea imprinted resin synthesized by the method has large adsorption capacity, is easy to separate from a solution, can be eluted after separation, and can be recycled after elution.
The thiourea imprinted resin can be used for adsorbing gold, and the adsorption quantity can be adjusted by controlling the acid-base condition.
Drawings
FIG. 1 is an adsorption isotherm of Au (III) ions by Au-TUCS resin and NI-TUCS resin, with the abscissa representing the concentration of residual gold ions in the supernatant and the ordinate representing the amount of gold ions adsorbed in the resin;
FIG. 2 shows the effect of different amounts of glutaraldehyde on the adsorption performance of thiourea-imprinted resins;
FIG. 3 is a graph showing the effect of different cross-linking times on adsorption performance of thiourea-imprinted resins;
FIG. 4 shows the effect of different gold ion dosages on the adsorption performance of thiourea-imprinted resins;
FIG. 5 influence of pH on adsorption performance of Thiourea imprinted resins.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation process of the thiourea imprinted resin comprises the following steps:
And 2, adding a certain amount of water, thiourea and glutaraldehyde into a four-neck flask, and stirring for a period of time at 50 ℃. Adding chitosan gel particles into the four-neck flask, stirring at 70 ℃ for crosslinking reaction, stopping stirring, cooling to room temperature, washing the obtained product with absolute ethyl alcohol and distilled water, oscillating with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10 hours, eluting with the eluent until gold ions on the product are completely eluted when the product is detected by 1M sodium sulfide solution, washing to be neutral, and drying at 50 ℃ to obtain the thiourea imprinted resin (Au-TUCS).
Wherein the dosage ratio of the chitosan, the gold ions and the glutaraldehyde is as follows: 1g (0.055-0.277) mmol (4-9) mL. The concentration of imprinting ions Au in the gold ion solution is 200-1000 mg/L. Gold ion solution chloroauric acid solution.
In the step 2, the crosslinking time is 2-8 h.
The method for adsorbing Au in the solution by using the thiourea imprinted resin comprises the following steps:
(1) adding thiourea imprinted resin into the solution containing gold ions, and then oscillating for 4h at 28 ℃ to adsorb the gold ions in the solution by using the thiourea imprinted resin. The ratio of the thiourea imprinted resin to the Au solution is (0.01-0.03 g): 20 mL.
(2) After adsorption, carrying out centrifugal separation or filtration to obtain thiourea imprinted resin for adsorbing gold;
(3) and eluting the adsorbed thiourea imprinted resin with an eluent, washing to be neutral, drying, and reusing the resin for adsorbing gold in the solution.
The present invention is described in further detail below with reference to examples:
example 1: comparison of thiourea imprinted resin with Au in non-imprinted resin adsorption solution, and comparison of thiourea imprinted resin with Au in other imprinted resin adsorption solution
Preparation of thiourea imprinted resins:
weighing 1g of chitosan, adding 50mL of chitosan with the concentration of 600mL & L-1Adding chloroauric acid solution, stirring, adding glacial acetic acid until the mass concentration of glacial acetic acid is 2%, stirring at 50 deg.C for 4 hr to form gel, washing with 0.5M sodium hydroxide, removing excessive gold ions, and washing to neutrality.
In a four-necked flask, a certain amount of water was added, and 0.5g of thiourea and 15mL of 50% glutaraldehyde were weighed and stirred at 50 ℃ for 4 hours. Adding gel particles of chitosan into a four-neck flask, stirring for 6h at 70 ℃, stopping stirring, cooling to room temperature, washing with absolute ethyl alcohol and distilled water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10h, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to neutrality. Drying at 50 deg.C.
Preparation of non-imprinted resin (NI-TUCS):
chitosan 1g was weighed into 50mL of deionized water and stirred with glacial acetic acid (2%) at 50 deg.C for 4h to form a gel which was then washed to neutrality with 0.5M NaOH solution.
In a four-necked flask, 50mL of deionized water was added, and 0.5g of thiourea and 15mL of 50% glutaraldehyde were weighed and stirred at 50 ℃ for 4 hours. Adding gel particles of chitosan into a four-neck flask, stirring at 70 ℃ for 6h, stopping stirring, cooling to room temperature, washing with absolute ethyl alcohol and distilled water, and drying at 50 ℃.
Respectively adsorbing gold ions in the chloroauric acid solution by using the prepared thiourea imprinted resin and the non-imprinted resin, filtering, taking supernate, and measuring the gold content by adopting flame atomic absorption.
The result of flame atomic absorption detection is shown in figure 1, and the adsorption amount of thiourea imprinted resin to gold in the solution is doubled compared with that of non-imprinted resin. The imprinting has obvious advantages compared with non-imprinting, because the imprinting cross-links, the cavity structure which can specifically identify Au (III) is formed on the surface of Au-TUCS, functional groups which can effectively combine Au (III) are reserved in the cavity structures, and the imprinting has specific identification performance on Au (III); on the other hand, after crosslinking, although the content of amino groups on the resin is reduced, the crystal structure is weakened to a certain extent, so that the hydrogen bonding action between the amino groups and hydroxyl groups on the molecular chain is weakened, the activity of adsorption sites is relatively increased, and Au (III) is more easily bonded.
Example 2: influence of different concentrations of acetic acid solution on adsorption performance of thiourea imprinted resin
The preparation process comprises the following steps:
adding 2g of thiourea into a four-mouth bottle, adding 50mL of deionized water, adding 50% of glutaraldehyde, respectively, and reacting for 4 hours at 50 ℃.
Adding 50mL of chitosan with the concentration of 600mL & L into 1g of chitosan-1The three groups of experiments are carried out in parallel by adding glacial acetic acid into the chloroauric acid solution and enabling the mass concentration of the glacial acetic acid to be 1%, 2% and 3%, blotting is carried out for 4 hours at 50 ℃, the solution is treated into gel particles by sodium hydroxide with the concentration of 0.5mol/L, and the gel particles are washed to be neutral by deionized water.
Adding chitosan gel particles into the four-mouth bottle, stirring for 6h at 70 ℃, washing with absolute ethyl alcohol and deionized water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10h, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to be neutral. Drying at 50 deg.C.
Adding 0.01g of thiourea blotting resin into 20mL of Au solution, then utilizing the method of adsorbing Au in the solution by the thiourea blotting resin, oscillating for 4h at 28 ℃, filtering, taking supernatant, and measuring the gold content by adopting flame atomic absorption.
Flame atomic absorption is used for sample measurement, and the result shows that when the concentration of the chitosan acetic acid is 1%, the solidification is slow, and the balling property of gel particles is poor; when the concentration of the chitosan acetic acid is 2%, the solidification is fast, and the gel particles are smooth and loose, thereby being beneficial to adsorption; when the concentration of the chitosan acetic acid is 3%, the solidification is fast, and the gel particles are firm and compact. Wherein when the concentration of acetic acid is 2%, the maximum adsorption amount of the resin is 4.82 mmol.L-1Thus, the concentration of the optimal acetic acid solution selected by the present invention is 2%.
Example 3: influence of different glutaraldehyde dosage on adsorption performance of thiourea imprinted resin
The cross-linking agent has an important function on the resin to form an imprinting cavity, and is beneficial to fixing imprinting Au (III) to form a rigid polymer with an imprinting cavity structure. Because acid groups are arranged at two ends of a glutaraldehyde molecular chain, the glutaraldehyde molecular chain can react with amino groups of chitosan to link the molecular chain of the chitosan to form a reticular polymer. Glutaraldehyde is therefore the ideal crosslinker of choice.
The preparation process comprises the following steps:
in a four-mouth bottle, 3g of thiourea is added, 50mL of deionized water is added, 50% of glutaraldehyde is added, the volume of the added solution is 8mL, 10 mL, 12mL, 14 mL, 16 mL and 18mL respectively, parallel experiments are carried out, and the reaction is carried out for 4 hours at 50 ℃.
Adding 50mL of chitosan with the concentration of 600mL & L into 1g of chitosan-1Adding 1mL of glacial acetic acid into the chloroauric acid solution, stirring, adding 1mL of glacial acetic acid, allowing the mass concentration of the glacial acetic acid to be 2%, performing blotting at 50 ℃ for 4h, treating the mixture with 0.5mol/L sodium hydroxide to form gel particles, and washing the gel particles to be neutral by using deionized water.
Adding chitosan gel particles into the four-mouth bottle, stirring for 6h at 70 ℃, washing with absolute ethyl alcohol and deionized water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10h, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to be neutral. Drying at 50 deg.C.
Adding 0.01g of thiourea blotting resin into 20mL of Au solution, then utilizing the method of adsorbing Au in the solution by the thiourea blotting resin, oscillating for 4h at 28 ℃, filtering, taking supernatant, and measuring the gold content by adopting flame atomic absorption.
The results of the measurement by flame atomic absorption are shown in FIG. 2, and it can be seen that the formed imprinted cavity is increased and the adsorption capacity is increased with the increase of the amount of glutaraldehyde. The subsequent decrease is due to the fact that as glutaraldehyde is increased, the imprinted cavity is maximized, the effective adsorption sites in the thiourea imprinted resin are reduced, and the adsorption capacity is reduced. Thus, in the case of 1g of chitosan, the optimal amount of 50% glutaraldehyde used during the synthesis was 12 mL.
Example 4: effect of different crosslinking time on adsorption Properties of Thiourea imprinted resins
3g of thiourea was added into a four-necked flask, 50mL of deionized water was added, 12mL of 50% glutaraldehyde was added, and the mixture was reacted at 50 ℃ for 4 hours.
Adding 50mL of chitosan with the concentration of 600mL & L into 1g of chitosan-1Adding 1mL of glacial acetic acid into the chloroauric acid solution, stirring, adding glacial acetic acid to make the mass concentration of glacial acetic acid be 2%, blotting at 50 deg.C for 4h, and adding 0.5mol/L oxyhydrogenThe sodium chloride is treated into gel particles, and the gel particles are washed to be neutral by deionized water.
Adding chitosan gel particles into a four-mouth bottle, stirring for 2, 3, 4, 5, 6 and 7 hours at 70 ℃, washing with absolute ethyl alcohol and deionized water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10 hours, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to be neutral. Drying at 50 deg.C.
Adding 0.01g of thiourea blotting resin into 20mL of Au solution, then oscillating for 4h at 28 ℃ by utilizing a method of adsorbing Au in the solution by using the thiourea blotting resin, taking supernate, and measuring the gold content by adopting flame atomic absorption.
The result of the sample measurement by flame atomic absorption is shown in fig. 3, and it can be seen from the figure that, as the crosslinking time increases before 5h, the more fully the amino group of chitosan reacts with the aldehyde group of glutaraldehyde, the formed imprinted cavity increases, so that the adsorption amount increases, 5h is fully crosslinked, the formed imprinted amount reaches the maximum, and then most of the amino group continues to be crosslinked to react with the crosslinking agent, and the ability of combining Au (III) is lost, so that the content of the amino group on the resin decreases, the adsorption capacity decreases, and the optimal crosslinking time is 5 h.
Example 5: influence of different gold ion dosages on adsorption performance of thiourea imprinted resin
3g of thiourea was added into a four-necked flask, 50mL of deionized water was added, 12mL of 50% glutaraldehyde was added, and the mixture was reacted at 50 ℃ for 4 hours.
Adding 1g of chitosan into 50mL of chloroauric acid solutions with different concentrations of 218.6, 437.2, 546.5, 655.8, 874.4 and 1093mg/L respectively, stirring, adding 1mL of glacial acetic acid to ensure that the mass concentration of the glacial acetic acid is 2%, carrying out imprinting for 4h at 50 ℃, treating the mixture into gel particles by using sodium hydroxide with the concentration of 0.5mol/L, and washing the gel particles to be neutral by using deionized water.
Adding chitosan gel particles into a four-mouth bottle, stirring for 6 hours at 70 ℃, washing with absolute ethyl alcohol and deionized water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10 hours, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, washing to be neutral, and drying at 50 ℃.
Adding 0.01g of thiourea blotting resin into 20mL of Au solution, then oscillating for 4h at 28 ℃ by utilizing a method of adsorbing Au in the solution by using the thiourea blotting resin, taking supernate, and measuring the gold content by adopting flame atomic absorption.
The results of the flame atomic absorption measurements are shown in FIG. 4, which shows that the increase in the concentration of Au (III) gradually increases the adsorption capacity of the thiourea-imprinted resin. It is shown that the increase of the number of the imprinting Au (III) increases the number of the imprinting holes formed on the thiourea imprinting resin, thereby improving the selective adsorption capability of Au (III). When the concentration of Au (III) is less than 655mg/L, all amino groups of chitosan are not combined with Au (III), the formed imprinting holes are increased along with the increase of the concentration of Au (III), the adsorption amount is increased, and after crosslinking, the adsorption capacity is reduced when the concentration of Au (III) is more than 655 mg/L.
Example 6: synthesis under optimum conditions
Adding 50mL of chitosan with the concentration of 650mL & L into 1g of chitosan-1Adding 1mL of glacial acetic acid into the chloroauric acid solution, stirring at 50 ℃ for 4h to make the mass concentration of the glacial acetic acid be 2%, treating the mixture with 0.5M sodium hydroxide (150mL) to form gel particles after the gel is formed, washing with water to remove excessive gold ions, and washing to be neutral.
In a four-necked flask, 50mL of water, 3g of thiourea, 12mL of 50% glutaraldehyde were added, and the mixture was stirred at 50 ℃ for 3 hours. Adding chitosan gel particles into the four-neck flask, stirring for 5h at 70 ℃, stopping stirring, cooling to room temperature, washing with absolute ethyl alcohol and distilled water, oscillating the resin with an eluent (0.5M thiourea +1M sulfuric acid solution) at 28 ℃ for 10h, eluting with the eluent until detection with 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to neutrality. Drying at 50 deg.C.
Example 7: influence of pH on adsorption Properties of Thiourea imprinted resins
20mL of chloroauric acid solution with the concentration of 350mg/l is taken, the pH of the solution is adjusted to be 1, 2, 3, 4, 5, 6 and 7 respectively by using 2M sodium hydroxide or 1M hydrochloric acid, 10mg of synthetic thiourea imprinted resin is added respectively, the solution is oscillated for 4 hours at the temperature of 28 ℃, and the solution is filtered and the concentration of gold ions in the filtrate is detected by flame atomic absorption.
The control experiment was performed in the same manner by replacing the thiourea-imprinted resin with the non-imprinted resin.
As shown in fig. 5, it can be seen that the adsorption amount of the thiourea imprinted resin is higher than that of the non-imprinted resin under different pH conditions, and the adsorption amount of both the thiourea imprinted resin and the non-imprinted resin is reduced with the increase of pH, so that the thiourea imprinted resin has a better adsorption effect on Au in a solution under an acidic condition.
Example 8: recycling of thiourea imprinted resins
And (2) taking 20mL of chloroauric acid solution with the concentration of 350mg/l, adding 10mg of synthesized thiourea imprinted resin, oscillating for 4h at 28 ℃, filtering, oscillating the adsorbed resin for 10h at 28 ℃ by using an eluent (0.5M thiourea +1M sulfuric acid solution), eluting by using the eluent until detection by using 1M sodium sulfide solution shows that gold ions on the thiourea imprinted resin are completely eluted, and washing to be neutral. Drying at 50 deg.C. 20mL of chloroauric acid solution with the concentration of 350mg/l is taken, 10mg of eluted thiourea imprinted resin is added, the mixture is shaken for 4 hours at the temperature of 28 ℃, and then is filtered, and the concentration of gold ions in the filtrate is detected by flame atomic absorption. Au-TUCS vs. Au Cl4 –The adsorption amount of the thiourea resin is basically kept unchanged, and is reduced from 3.27 at the 1 st time to 3.19mg/g at the 2 nd time by only 2.45 percent, which fully indicates that the thiourea resin has excellent repeated use performance.
The results are shown in table 1, and it can be seen that the adsorption amount of the thiourea imprinted resin of the invention is obviously improved compared with the prior art.
TABLE 1 adsorption of Au (III) by different adsorbents
[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]Amidonized modified D301 resin vs Au Cl, respectively4 –Adsorption and discrimination Performance of [ J]Functional material, 2016, 47(9): 9220-9225.
[3]Yuanxiaxia, Zhangwan, Douqui, etc. silica gel surface Au Cl4 –Preparation of imprinted polyethyleneimine and research on recognition characteristics [ J]Noble metals 2015, 36(2): 1-8.
Claims (7)
1. The preparation method of the thiourea imprinted resin is characterized by comprising the following steps:
step 1, adding chitosan into a gold ion solution, adding glacial acetic acid to obtain a solution A, stirring to form gel, treating the gel into gel particles by using a sodium hydroxide solution, and washing to obtain chitosan gel particles; adding thiourea and glutaraldehyde into water, and stirring for reaction to obtain a solution B;
step 2, adding chitosan gel particles into the solution B, stirring for cross-linking reaction, washing the obtained product, eluting with an eluent, washing, and drying to obtain thiourea imprinted resin;
in the step 1, the dosage ratio of chitosan, gold ions, glutaraldehyde and thiourea is as follows: 1g (0.055-0.277) mmol: (4-9) mL: (0.5-3) g;
in the step 1, the mass fraction of the glacial acetic acid in the solution A is 1-3%;
in the step 1, the solution A is stirred at 50 ℃ to form gel, and the thiourea and the glutaraldehyde are stirred and reacted at 50 ℃ to obtain a solution B.
2. The preparation method of the thiourea imprinted resin according to claim 1, wherein in the step 2, the crosslinking reaction temperature is 70 ℃ and the time is 2-8 h.
3. The method for preparing thiourea imprinted resin according to claim 1, wherein in the step 2, the elution is specifically: the eluent is a mixed solution of thiourea and sulfuric acid.
4. The thiourea-imprinted resin prepared by the preparation method according to any one of claims 1 to 3.
5. Use of the thiourea imprinted resin of claim 4 for adsorbing gold.
6. Use according to claim 5, characterized in that it comprises the following steps:
(1) adding thiourea imprinted resin into the solution containing the gold ions, oscillating, and adsorbing the gold ions in the solution by using the thiourea imprinted resin;
(2) and after adsorption, centrifugal separation or filtration is carried out.
7. The use according to claim 6, characterized in that in step (1) the solution containing gold ions is adjusted to a pH in the range of 1-7 and is subjected to adsorption.
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