KR101871636B1 - Method for preparing heavy metal ions imprinted absorbent for the selective separation of heavy metal ions - Google Patents
Method for preparing heavy metal ions imprinted absorbent for the selective separation of heavy metal ions Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
Abstract
Description
The present invention relates to a method for producing an adsorbent having a heavy metal ion ion capable of selectively separating heavy metal ions.
IIT (ion imprinting technology) is a state-of-the-art technology that selectively recognizes target ions in an aqueous medium using ion-imprinted sorbents. Polymerization techniques are used to prepare ion-imprinted polymers through polymerization of functional monomers around template ions. After polymerization, the template ions are extracted from the polymer matrix through an elution process, thereby creating a bonding cavity for the target ion.
Since the conjugate cavity can only intercalate the same morphologically identical template ion and can not interfere with molecules having a different stereostructure than the template ion, a polymer having a template ionic space can be used to separate template ions and other molecules . This is because Fischer's Lock-and-Key Concept, in which an antibody formed against an antigen selectively interacts with an antigen, or the Receptor Theory in which an enzyme in a living body is only active against a specific substrate It is. Accordingly, when preparing an ion-insoluble polymer through such a method, the desired heavy metals and the like can be selectively adsorbed and removed in water.
However, conventional ionic imprinting techniques have some disadvantages including incomplete removal of template ions, diffusion barrier formation, low binding capacity, slow mass transfer and slow binding kinetics.
Therefore, there is an urgent need to study a technique for producing an adsorbent having a high heavy metal loading capability and a high heavy metal removal capability overcoming the above disadvantages.
The present invention has been conceived to solve the problems of the prior art described above, and it is an object of the present invention to provide a method for producing a heavy metal adsorbent by forming a heavy metal adsorption site on a surface of a support and adding an appropriate amount of halogen ion together when the heavy metal ion is loaded, Thereby providing an adsorbent.
In order to achieve the above object,
The present invention
1) reacting a silane-based compound on a support comprising silica to bond the silane-based compound to the support;
2) reacting the amine-based compound on the support to which the silane-based compound is bound, thereby binding the amine-based compound to the silane-based compound;
3) adding a heavy metal ion and a halogen ion to a support to which the silane-based compound bonded with the amine compound of 2) is bound, and loading heavy metal ions on the support;
4) adding a crosslinking agent to the support loaded with the heavy metal ions of the above 3) and reacting; And
5) washing the crosslinked support of 4) with an acid solution to remove the heavy metal ions, thereby forming a heavy metal selective adsorption site on the support;
The present invention provides a method for producing heavy metal ion imprinted adsorbents.
In one embodiment of the present invention, the molar concentration ratio of the halogen ion to the heavy metal ion in the above 3) may be 10 to 700.
In one embodiment of the present invention, the heavy metal may be at least one selected from the group consisting of Cu, Pb, Zn, Ni, Co, Cr, Al, Pt, Rh, Pd, Zr and Ir.
In one embodiment of the present invention, the silane-based compound is selected from the group consisting of (3-chloropropyl) trimethoxysilane, (3-chloroisobutyl) methoxysilane, (p- chloromethyl) phenyltrimethoxysilane, ) Triethoxysilane, (11-chloroundecyl) triethoxysilane, and (chloromethyl) trimethoxysilane.
In one embodiment of the present invention, the amine-based compound may be at least one selected from the group consisting of polyethyleneimine, norespermidine, spermidine and spermine.
In one embodiment of the present invention, the halogen ion may be Cl - .
In one embodiment of the present invention, the heavy metal selective adsorption point in 5) may be formed on the surface of the support.
In one embodiment of the present invention, the crosslinking agent may be ethylene glycol diglycidyl ether.
In one embodiment of the present invention, the support comprising silica may be mesoporous silica.
Further, according to the present invention,
1) reacting mesoporous silica with (3-chloropropyl) trimethoxysilane to bind (3-chloropropyl) trimethoxysilane to the mesoporous silica surface;
2) reacting the (3-chloropropyl) trimethoxysilane-bonded mesoporous silica of 1) with polyethyleneimine to bind polyethyleneimine to the (3-chloropropyl) trimethoxysilane;
3) The above 2) polyethyleneimine combination of 3-chloropropyl) trimethoxysilane in the mesoporous silica are combined, [Cl -] / [Cu 2+] =
4) adding ethylene glycol diglycidyl ether as a crosslinking agent to the mesoporous silica loaded with Cu 2+ in the above 3) and reacting; And
5) forming a selective adsorption points Cu 2+ in the mesoporous silica surface, by washing with an acid to a mesoporous silica and removing the cross-linking solution in the Cu 2+ 4);
The present invention also provides a method for producing an adsorbent for heavy metal ion impregnation.
The method of producing heavy metal ion impregnated adsorbent according to the present invention is economical because it can minimize the input and loss of the heavy metal and maximize the load in heavy metal ion loading process by providing the optimum manufacturing conditions, So that the selective adsorption characteristic to the target heavy metal is overwhelmingly increased.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of the synthesis of mesoporous silica with a Cu ionic imprint.
FIG. 2 is a diagram showing FESEM results and EDX results for analyzing the surface morphology and element composition of PEI-mesoporous silica and PEI-mesoporous silica which are Cu ion-striking.
3 is a graph showing the effect of the [Cl - ] / [Cu (II)] ratio of Cu (II) load on PEI-mesoporous silica.
4 is in a divalent metal ion conditions, different synthesis conditions ([Cl -] / [Cu (Ⅱ)] ratio of 2 to 1000) is a diagram showing the experimental results of Cu-selective ion engraved PEI- mesoporous silica produced in .
5 shows selectivity results of PEI-mesoporous silica, which is a Cu ion ion prepared under various synthesis conditions ([Cl - ] / [Cu (II)] ratio = 2 to 1000) under the condition of trivalent / Fig.
Hereinafter, preferred embodiments of the present invention will be described in order to explain the present invention more specifically. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms.
The present invention
1) reacting a silane-based compound on a support comprising silica to bond the silane-based compound to the support;
2) reacting the amine-based compound on the support to which the silane-based compound is bound, thereby binding the amine-based compound to the silane-based compound;
3) adding a heavy metal ion and a halogen ion to a support to which the silane-based compound bonded with the amine compound of 2) is bound, and loading heavy metal ions on the support;
4) adding a crosslinking agent to the support loaded with the heavy metal ions of the above 3) and reacting; And
5) washing the crosslinked support of 4) with an acid solution to remove the heavy metal ions, thereby forming a heavy metal selective adsorption site on the support;
The present invention also provides a method for producing an adsorbent for heavy metal ion impregnation.
Specifically, in one embodiment of the present invention, a silane compound, specifically, (3-chloropropyl) trimethoxysilane is bonded to the surface of the mesoporous silica (including the surface of the pore) as a support, An amine-based compound, specifically, a polyethyleneimine, may be bonded.
The term "bond" may include physical, chemical attachment, linkage, and the like.
In the surface stamping technique, the silica is a support which can be suitably used due to its physico-chemical and thermal stability and high reusability.
The target heavy metal ions desired to be adsorbed can be loaded into the silica to which the amine compound is bonded, and at the same time, an appropriate amount of the halogen ion can be added at the same time.
Thereafter, a crosslinking agent is added to form a crosslinking site of the heavy metal, and the unreacted crosslinking agent and the heavy metal may be removed from the silica by washing with an acid solution, preferably hydrochloric acid. Accordingly, the crosslinked region from which heavy metal ions have been removed can be formed as an adsorption site capable of selectively adsorbing the same heavy metal thereafter.
In one embodiment of the present invention, the molar concentration ratio of the halogen ion to the heavy metal ion in the above 3) may be 10 to 700, and may be 300 to 700. The molar concentration ratio of the halogen ion to the heavy metal ion may mean [halogen ion] / [heavy metal ion]. When the molar concentration ratio is higher than the above range, the ratio of the heavy metal ions forming the complex is increased rather than the desired heavy metal ion (ions in which the heavy metal ions are solitarily dissociated), and the selectivity to the desired heavy metal ion may decrease. Also, if the molar concentration ratio is lower than the above-mentioned range, the halogen ion may be small and it may not affect the selectivity in the load.
In one embodiment of the present invention, the heavy metal may be at least one selected from the group consisting of Cu, Pb, Zn, Ni, Co, Cr, Al, Pt, Rh, Pd, Zr and Ir, .
In one embodiment of the present invention, the silane-based compound is selected from the group consisting of (3-chloropropyl) trimethoxysilane, (3-chloroisobutyl) methoxysilane, (p- chloromethyl) phenyltrimethoxysilane, ) Triethoxysilane, (11-chloroundecyl) triethoxysilane, and (chloromethyl) trimethoxysilane.
In one embodiment of the present invention, the amine-based compound may be at least one member selected from the group consisting of polyethyleneimine, norfemiridine, spermidine and spermine, and specifically may be polyethyleneimine. The polyethyleneimine is a cationic polyamine having a large number of primary, secondary and tertiary amine groups. Polyethyleneimine has high adsorption capacity through strong chelating with transition metal (Cu, Ni, Co, Mo, Fe, Cd, Pb, Pt, Rh, Pd, Zr, Ir etc.) It may be used by being fixed to a support.
In one embodiment of the present invention, the halogen ion may be Cl - .
In one embodiment of the present invention, the heavy metal selective adsorption point in 5) may be formed on the surface of the support. When the adsorption site is formed on the surface of the silica by forming the adsorption site on the surface, the limit of the adsorption rate can be overcome because the heavy metal ions are difficult to penetrate into the inside.
In one embodiment of the present invention, the crosslinking agent may be ethylene glycol diglycidyl ether.
In one embodiment of the present invention, the support comprising silica may be mesoporous silica. Mesoporous may be meant to include pores having a diameter of 2 to 50 nm, but is not limited thereto.
Further,
1) reacting mesoporous silica with (3-chloropropyl) trimethoxysilane to bind (3-chloropropyl) trimethoxysilane to the mesoporous silica surface;
2) reacting the (3-chloropropyl) trimethoxysilane-bonded mesoporous silica of 1) with polyethyleneimine to bind polyethyleneimine to the (3-chloropropyl) trimethoxysilane;
3) The above 2) polyethyleneimine combination of 3-chloropropyl) trimethoxysilane in the mesoporous silica are combined, [Cl -] / [Cu 2+] =
4) adding ethylene glycol diglycidyl ether as a crosslinking agent to the mesoporous silica loaded with Cu 2+ in the above 3) and reacting; And
5) forming a selective adsorption points Cu 2+ in the mesoporous silica surface, by washing with an acid to a mesoporous silica and removing the cross-linking solution in the Cu 2+ 4);
The present invention also provides a method for producing an adsorbent for heavy metal ion impregnation.
Hereinafter, examples and experimental examples will be described to help understand the effects of the present invention. It should be noted, however, that the following description is only an example of the contents and effects of the present invention, and the scope and effect of the present invention are not limited thereto.
Example 1 Synthesis of Poly (ethyleneimine) - Mesoporous Silica with Cu Ion Angle
All chemicals used in the synthesis were purchased from Sigma Aldrich (St. Louis, MO) unless otherwise noted. A synthetic schematic view of a mesoporous silica having a Cu ion ion as an example of synthesis of the porous metal ion-bound porous silica of the present invention is shown in FIG.
Example 1-1. Synthesis of mesoporous silica
First, 16.0 mL of deionized water, 20 mL of 2M hydrochloric acid (HCl, 36.0%, Duksan Pure Chemical Co., Seoul), 10 mL of anhydrous ethanol (EtOH, 99.9% , 1.2 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 0.2 g of cetyltrimethylammonium bromide surfactant (CTAB, 99% or more) were prepared. The mixed solution of the above materials was stirred at room temperature for 45 minutes to form micelle rods. Then, 4 mL of tetraethyl orthosilicate (TEOS, 99% or more) was added to the solution with a silica precursor. After 45 minutes of crystallization with stirring, a white precipitate was obtained. The white precipitate was filtered through a 0.45 [mu] m membrane filter and washed with 2 L of deionized water to remove unreacted material and neutralize the pH. The washed precipitate was dried overnight under a desiccator and then calcined at 600 ° C for 6 hours to remove the remaining surfactant. After cooling, the mesoporous silica particles were obtained by fragmenting using a mortar and a pestle.
Examples 1-2. Synthesis of PEI-mesoporous silica
5 g of mesoporous silica and 100 mL of (3-chloropropyl) trimethoxysilane (97% or more) were reacted at 80 ° C for 6 hours while intermittently adding 1 mL of deionized water to obtain 3-chloropropyl-meso After preparing porous silica (CP-mesoporous silica), the CP-mesoporous silica was filtered and dried at 60 ° C overnight. After cooling, CP-mesoporous silica particles were obtained by fragmenting using a mortar and pestle. Then, 50 mL of PEI solution (50% H 2 O) and 1 g of CP-mesoporous silica were stirred at 90 ° C for 6 hours to prepare PEI-mesoporous silica. After the reaction, the obtained PEI-mesoporous silica was filtered, washed with deionized water and dried at 60 ° C overnight. After cooling, PEI-mesoporous silica particles were obtained by fragmenting into a mortar and pestle.
Examples 1-3. Synthesis of Cu ion-imprinted PEI-mesoporous silica
The Cu ion engraved PEI- prepared prior mesoporous silica, Cu (Ⅱ) ion was load onto PEI- mesoporous silica, wherein the concentration of Cu (Ⅱ) was fixed at 1000 μM, [Cl -] / [Cu (II)] was 2, 50, 100, 200, 500 or 1000, respectively. The loading of Cu (II) to PEI-mesoporous silica was performed by adding 1 g of PEI-mesoporous silica to 1 L of NaCl and Cu (II) ion solution while stirring vigorously at 30 ° C for 6 hours. The Cu loaded PEI-mesoporous silica was filtered and dried at 60 < 0 > C overnight.
To prepare Cu ion-imprinted PEI-mesoporous silica, 1 g of Cu loaded PEI-mesoporous silica and 0.25 g of ethylene glycol diglycidyl ether (EGDE, Tokyo Chemical Industry Co., Tokyo, Japan) Was added to 50 mL of absolute ethanol and allowed to react at 25 DEG C for 4 hours with continued stirring. After the reaction, the particles were washed with 1 L of 0.1 M HCl solution to remove the Cu (Ⅱ) ions and the unreacted EGDE, and the pH was neutralized by washing with deionized water. The particles were filtered and dried at 60 < 0 > C overnight. After cooling, Cu ion-imprinted PEI-mesoporous silica was obtained by fragmenting into a mortar and pestle.
EXPERIMENTAL EXAMPLE 1 Evaluation of surface morphology and element composition of PEI-mesoporous silica, Cu-loaded PEI-mesoporous silica and Cu ion-imprinted PEI-mesoporous silica
(FESEM, Supra 55VP, Carl Zeiss, Oberkochen, Germany) and energy dispersive X-ray spectroscopy (EDX) were used to analyze the surface morphology and elemental composition of the Cu ion-imprinted PEI-mesoporous silica and PEI-mesoporous silica. , AURIGA, Carl Zeiss) were used.
FESEM results and EDX results for analyzing the surface morphology and element composition of Cu ion-imprinted PEI-mesoporous silica and PEI-mesoporous silica are shown in FIG.
As shown in Fig. 2, PEI-mesoporous silica (a) is well adhered to PEI-coated surface, and Cu-loaded PEI-mesoporous silica (b) exhibits a surface loaded with Cu. Also, the surface of the Cu ion-grafted PEI-mesoporous silica (c) was similar to the surface of the PEI-mesoporous silica because the Cu (II) ion was removed from the surface of the Cu loaded PEI-mesoporous silica during the imprinting process, Can be confirmed.
According to the EDX results, the N peak (K ? = 0.392 keV, K ? = 0.400 keV) of PEI in the PEI-mesoporous silica (d) (L α = 0.930 keV), and after the imprinting process, the Cu (Ⅱ) peak disappeared in the PE ion mesoporous silica (f).
According to the above FESEM and EDX results, it can be seen that PEI is adhered to the mesoporous silica, Cu is loaded, and Cu is separated after imprinting.
EXPERIMENTAL EXAMPLE 2 Preparation of ([Cl - ] / [Cu (Ⅱ)]]
The effect of [Cl - ] / [Cu (II)] ratio of Cu (Ⅱ) load on PEI-mesoporous silica is shown in Table 1 and FIG.
As shown in Table 1 and 3, [Cl -] - load as / [Cu (Ⅱ)] is increased / [Cu (Ⅱ)] = 2 the load is was about 76.66 μmol / g, [Cl] And the loadings were 154.05, 140.25 and 134.35 μmol / g for [Cl - ] / [Cu (Ⅱ)] = 200, 500 and 1000, respectively.
Based on the addition of NaCl, it can be seen that the load of the transition metal is enhanced based on the following equation.
[Equation 2] The distribution coefficient between the transition metal ion and the hydrogen ion of n-valence
[Equation 3] The distribution coefficient between the transition metal ion and the hydrogen ion of n is summarized based on the above two relations
In the above equation, since Keq is a constant, α Me / H is proportional to the concentration of Cl - . Based on this, α Me / H is increased by addition of NaCl under the same concentration of transition metal, It can be seen that
The addition of NaCl improves the Cu loading, but it is difficult to ensure Cu selectivity when [Cl - ] / [Cu (Ⅱ)] = 1000. This is because the addition of Cl - It seems to be caused by.
Experimental Example 3 Evaluation of Cu (Ⅱ) selectivity according to Cu ion imprinting
Cu (Ⅱ) selectivity experiments were carried out under batch conditions to characterize PEI-mesoporous silica and Cu ion-imprinted PEI-mesoporous silica in Cu (Ⅱ) adsorption. All batch experiments were performed 3 times at 30 < 0 > C. (0.1 M) prepared from copper (II) chloride dihydrate (CuCl 2 .2H 2 O, EP grade, Duksan Chemical) was diluted to prepare a Cu (II) solution having a desired concentration.
pH experiments were performed in a 50 mL polypropylene conical tube containing PEI-mesoporous silica (adsorbent capacity = 1 g / L) and Cu (II) ion (initial concentration = 1000 μM) Respectively. The pH of the solution was adjusted from 2 to 5 using 0.1 M NaOH and 0.1 M HCl solution. After 24 hours of reaction, the sample was collected and filtered through a 0.45 [mu] m membrane filter. The concentration of Cu (Ⅱ) was analyzed using an inductively coupled plasma emission spectrometer (iCAP 7200 ICP-OES Duo, Thermo Fisher Scientific, Waltham, MA, USA). The Cu (II) adsorption capacity (q, μmol / g) of the adsorbent can be calculated by the following equation (4).
&Quot; (4) "
C i is the concentration of Cu (Ⅱ) in the aqueous phase before the adsorption reaction, C f is the concentration of Cu (Ⅱ) in the aqueous phase after the adsorption reaction, and C a is the amount of adsorbent.
Cu (Ⅱ) selectivity experiments were carried out in a multiple solution containing binary metal containing Cu (Ⅱ), Pb (Ⅱ), Zn (Ⅱ), Ni (Ⅱ) and Co (Ⅱ) CuCl 2 · 2H 2 O, lead chloride (Ⅱ) (PbCl 2 ≥98% ), zinc chloride (Ⅱ) (ZnCl 2 ≥98% ), nickel chloride (Ⅱ) hexahydrate (NiCl 2 · 6H 2 O, ≥96 %) And cobalt (II) chloride hexahydrate (CoCl 2 .6H 2 O, ≥95%). The solution pH was adjusted to 5 with 0.1 M HCl and 0.1 M NaOH solution. Cu (Ⅱ) selectivity experiments were performed under batch conditions (adsorbent capacity = 1 g / L). 30 mg of each sorbent (PEI-mesoporous silica and Cu ion-imprinted PEI-mesoporous silica) was added to a 50 mL conical tube containing 30 mL of a multicomponent metal solution. The solution was shaken in a shaking incubator at 120 rpm for 6 hours. After the reaction, the sample was collected and filtered through a membrane filter. The metal concentrations were analyzed using ICP-OES. (II) in a multicomponent solution containing trivalent / tetravalent metal ions (Cr (Ⅲ), Al (Ⅲ), and Zr (Ⅳ)) with Cu (Ⅱ) Selectivity experiments were performed. Multi-component metal solution (each metal concentration = 200 uM) is CuCl 2 · 2H 2 O, chloride, chromium (Ⅲ) hexahydrate (CrCl 3 · 6H 2 O, 96%), aluminum chloride (Ⅲ) hexahydrate (AlCl 3 · 6H 2 O, 99%) and zirconium (IV) chloride (ZrCl 4 , ≥99.5%).
The distribution coefficient (k d ) for the metal ion in the selectivity experiment can be determined using the following equations (5) and (6).
&Quot; (5) "
&Quot; (6) "
Based on the distribution coefficient, the Cu (II) selectivity (α) and the relative Cu (II) selectivity can be calculated using the following equations (7) and (8).
&Quot; (7) "
&Quot; (8) "
Cu (Ⅱ) adsorption on Cu ion-imprinted PEI-mesoporous silica was performed as a function of reaction time (initial Cu (Ⅱ)
Under divalent metal ion conditions, various synthesis conditions ([Cl - ] / [Cu (II)] Fig. 4 shows the selectivity test results of PEI-mesoporous silica, which is Cu ion imprinted at a ratio of 2 to 1000.
As shown in FIG. 4, the adsorption of Cu (II) showed a tendency to increase as the ratio of [Cl - ] / [Cu (II)] increased from 2 to 500 and decreased at a ratio of 1000. At a ratio of 2 to 500, adsorption of Zn (II), Ni (II) and Co (II) is negligible. The selectivity of Cu (Ⅱ) / Me (Ⅱ) selectivity (Cu (Ⅱ) / Me (Ⅱ) selectivity) increased from 2 to 500 in the given experimental conditions (molar concentration of divalent ions = 200 μM, pH = 5) Respectively. The adsorption of Cu (Ⅱ) on the Cu ion imprinted PEI-mesoporous silica at the ratio of 500 was highest (42.51 μmol / g) in the divalent ions. Cu (Ⅱ) selectivity for Cu (Ⅱ) / Pb (Ⅱ), ∞ (Cu (Ⅱ) / Zn (Ⅱ), Cu (II) selectivity for Cu (Ⅱ) / Me (Ⅱ) was calculated to be 79.62, which is 29.24 times that of PEI-mesoporous silica.
Under the conditions of the trivalent / tetravalent metal ion, various synthesis conditions ([Cl - ] / [Cu (II)] Fig. 5 shows selectivity results of PEI-mesoporous silica, which is Cu ion imprinted at a ratio of 2 to 1000.
As shown in FIG. 5, Cu (II) adsorption increased with a rate increase from 2 to 500 and decreased at a rate of 1000. Cu (Ⅱ) adsorption was the highest (56.71 μmol / g) at 500 ratios at the given experimental conditions (molarity of trivalent / tetravalent ions = 200 μM, pH = 5). Cu (Ⅱ) selectivities for Cu (Ⅱ) / Al (Ⅲ), Cu (Ⅱ) / Cr (Ⅲ) and Cu (Ⅱ) / Zr (Ⅳ) were 1.50, 9.12 and 5.87, respectively. The Cu selectivity of PEI-mesoporous silica with Cu ion impurity was 3.40 (Cr (III), Al (III) and Zr (IV)) under the conditions of trivalent / tetravalent metal ions (Cr (III), Al (IV)), which is 3.96 times higher than that of PEI-mesoporous silica.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is within the scope of the present invention that component changes to such an extent that they can be coped evenly within a range that does not deviate from the scope of the present invention.
Claims (10)
2) reacting the amine-based compound on the support to which the silane-based compound is bound, thereby binding the amine-based compound to the silane-based compound;
3) adding a heavy metal ion and a halogen ion to a support to which the silane-based compound bonded with the amine compound of 2) is bound to load the heavy metal ions on the support;
4) adding a crosslinking agent to the support loaded with the heavy metal ions of the above 3) and reacting; And
5) washing the crosslinked support of 4) with an acid solution to remove the heavy metal ions, thereby forming a heavy metal selective adsorption site on the support;
Lt; / RTI >
Wherein the molar concentration ratio of the halogen ion to the heavy metal ion in the step 3) is 10 to 700.
Wherein the heavy metal is at least one heavy metal ion selected from the group consisting of Cu, Pb, Zn, Ni, Co, Cr, Al, Pt, Rh, Pd, Zr and Ir.
The silane-based compound is preferably selected from the group consisting of (3-chloropropyl) trimethoxysilane, (3-chloroisobutyl) methoxysilane, (p- chloromethyl) phenyltrimethoxysilane, (chloromethyl) triethoxysilane, -Chlorodecyl) triethoxysilane and (chloromethyl) trimethoxysilane. The method for producing an adsorbent according to claim 1,
Wherein the amine compound is at least one heavy metal ion selected from the group consisting of polyethyleneimine, norfemiridine, spermidine and spermine.
Wherein the halogen ion is Cl - phosphorus ion.
Wherein a heavy metal selective adsorption point is formed on the surface of the support in 5).
Wherein the cross-linking agent is ethylene glycol diglycidyl ether.
Wherein the support comprising silica is a mesoporous silica.
2) reacting the (3-chloropropyl) trimethoxysilane-bonded mesoporous silica of 1) with polyethyleneimine to bind polyethyleneimine to the (3-chloropropyl) trimethoxysilane;
3) The above 2) polyethyleneimine combination of 3-chloropropyl) trimethoxysilane in the mesoporous silica are combined, [Cl -] / [Cu 2+] = Cu 2+ , and Cl in a 300 to 700 molar concentration ratio - Adding Cu 2+ to the mesoporous silica;
4) adding ethylene glycol diglycidyl ether as a crosslinking agent to the mesoporous silica loaded with Cu 2+ in the above 3) and reacting; And
5) forming a selective adsorption points Cu 2+ in the mesoporous silica surface, by washing with an acid to a mesoporous silica and removing the cross-linking solution in the Cu 2+ 4);
≪ / RTI > wherein the adsorbent is a heavy metal ion.
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| CN109692666A (en) * | 2019-01-02 | 2019-04-30 | 复旦大学 | With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application |
| CN113694900A (en) * | 2020-05-22 | 2021-11-26 | 中南林业科技大学 | Lignin ion imprinting compound and preparation method and application thereof |
| CN115672290A (en) * | 2022-10-21 | 2023-02-03 | 浙江海洋大学 | Copper ion imprinted magnetic mesoporous silica composite material, preparation method and adsorption catalysis application thereof |
| KR20230030987A (en) | 2021-08-26 | 2023-03-07 | 한국원자력연구원 | Mesoporous ion-imprinted radioactive nuclide absorbent and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109692666A (en) * | 2019-01-02 | 2019-04-30 | 复旦大学 | With three teeth chelating adsorption site lead stamp mark silicon materials and its preparation method and application |
| CN109692666B (en) * | 2019-01-02 | 2021-09-17 | 复旦大学 | Lead imprinted silicon material with tridentate chelating adsorption sites and preparation method and application thereof |
| CN113694900A (en) * | 2020-05-22 | 2021-11-26 | 中南林业科技大学 | Lignin ion imprinting compound and preparation method and application thereof |
| KR20230030987A (en) | 2021-08-26 | 2023-03-07 | 한국원자력연구원 | Mesoporous ion-imprinted radioactive nuclide absorbent and preparing method thereof |
| KR102572837B1 (en) * | 2021-08-26 | 2023-08-30 | 한국원자력연구원 | Mesoporous ion-imprinted radioactive nuclide absorbent and preparing method thereof |
| CN115672290A (en) * | 2022-10-21 | 2023-02-03 | 浙江海洋大学 | Copper ion imprinted magnetic mesoporous silica composite material, preparation method and adsorption catalysis application thereof |
| CN115672290B (en) * | 2022-10-21 | 2024-01-26 | 浙江海洋大学 | Copper ion imprinting magnetic mesoporous silica composite material, preparation method and adsorption catalysis application thereof |
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