KR20150049194A - Chitosan bead and method for fabricating the same - Google Patents
Chitosan bead and method for fabricating the same Download PDFInfo
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- KR20150049194A KR20150049194A KR1020130129430A KR20130129430A KR20150049194A KR 20150049194 A KR20150049194 A KR 20150049194A KR 1020130129430 A KR1020130129430 A KR 1020130129430A KR 20130129430 A KR20130129430 A KR 20130129430A KR 20150049194 A KR20150049194 A KR 20150049194A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3221—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond the chemical bond being an ionic interaction
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Abstract
The present invention relates to a method for preparing a chitosan bead by immobilizing transition metal ions on chitosan beads and cross-linking chitosan molecules through transition metal ions, thereby improving the adsorption reactivity to phosphates, thereby effectively removing phosphates even in the presence of a low concentration of phosphate in water The present invention relates to a method for producing chitosan beads for removing phosphorus, which comprises the steps of preparing a chitosan solution by mixing chitosan powder having an amine group with an acid solution, and curing the chitosan solution to form chitosan beads And a step of mixing the chitosan beads with an aqueous solution of a transition metal hydrate to induce a chelate bond between the transition metal ion and the amine group, wherein the chelate bond of the transition metal ion and the amine group causes the chitosan polymer Is bridged by the transition metal ion, and the transition metal ion Characterized in that the functional group capable of binding function.
Description
The present invention relates to a chitosan bead for removing phosphorus, and more particularly, to a chitosan bead for immobilizing chitosan beads by immobilizing transition metal ions on chitosan beads and by crosslinking chitosan molecules through transition metal ions, The present invention relates to a chitosan bead for removing phosphorus, which can effectively remove phosphate even when phosphate is present in a low concentration, and a method for producing the chitosan bead.
In addition to nitrogen (N), phosphorus (P) is considered to be an essential nutrient for the growth of aquatic organisms and aquatic ecosystems, as well as water pollutants that directly affect the underwater eutrophication even at low concentrations in water have. Coagulation-sedimentation and biological treatment are widely used as a method of removing phosphorus in water, and recently, a method of removing phosphorus through an adsorbent (Korean Patent Publication No. 91-4018) has also been used.
The coagulation-precipitation method has advantages such as simplicity of process, high removal efficiency for high concentration phosphorus and relatively low treatment cost, but due to high initial installation cost, reduction of removal efficiency at low phosphorus concentration and necessity of additional process due to sludge formation There are many constraints. In addition, despite the advantages such as economic maintenance cost and effective removal efficiency for high concentration phosphorus, biological treatment has the effect of changing the removal efficiency depending on the initial influent conditions such as temperature and influent concentration, Is not excellent.
Accordingly, development of various types of adsorbents, which are effective for removing phosphorus at a low concentration, taking into consideration the ease of regeneration, installation and operation, and economical efficiency, is under development. However, the currently developed phosphorus-based organic-based adsorbent requires a complicated synthesis step for functionalization of the surface and has a weak physical strength. In the case of the inorganic-based adsorbent, the removal efficiency for the low concentration phosphorus is low There is a problem.
Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a chitosan bead in which a transition metal ion is immobilized on a chitosan bead and a chitosan molecule is crosslinked through a transition metal ion, The present invention provides a chitosan bead for removing phosphorus which can effectively remove phosphate even when it is present, and a method for producing the same.
In order to accomplish the above object, the present invention provides a method for producing chitosan beads for removing phosphorus, comprising the steps of: preparing a chitosan solution by mixing chitosan powder having an amine group into an acid solution; and curing the chitosan solution to form chitosan beads And a step of mixing the chitosan beads with an aqueous solution of a transition metal hydrate to induce a chelate bond between the transition metal ion and the amine group. By the chelate bond between the transition metal ion and the amine group, Is crosslinked by an ion, and the transition metal ion functions as a functional group capable of ligand bonding.
The transition metal hydrate is any one of cupric chloride (CuCl 2 .2H 2 O) and nickel chloride hydrate (NiCl 2 .6H 2 O). The concentration of dicarboxylic chloride (CuCl 2 .2H 2 O) in the aqueous solution of cupric chloride (CuCl 2 .2H 2 O) is 1 to 2 wt%. In the aqueous solution of nickel chloride hydrate (NiCl 2 .6H 2 O) The concentration of nickel chloride hydrate (NiCl 2 .6H 2 O) is 0.2 to 0.6 wt%. The pH of the aqueous solution of cupric chloride (CuCl 2 .2H 2 O) is 4 to 5, and the pH of the aqueous solution of nickel chloride hydrate (NiCl 2 .6H 2 O) is 5 to 7. In addition, the acid solution is a hydrochloric acid solution, and the concentration of the chitosan powder in the chitosan solution is 1 to 3 wt%.
In the step of curing the chitosan solution to form chitosan beads, the chitosan solution may be titrated into a NaOH solution to form chitosan beads. The chitosan powder may be deacetylated to 70-80% from chitin.
The chitosan bead for phosphorus removal according to the present invention is a cured product of a chitosan powder having an amine group, wherein the amine group forms a chelate bond with the transition metal, and the chelate bond of the transition metal ion and the amine group causes the chitosan polymer to react with the transition metal ion And is characterized in that the transition metal ion acts as a functional group capable of ligand bonding.
The chitosan beads for removing phosphorus according to the present invention and the manufacturing method thereof have the following effects.
In the chitosan beads, as the transition metal ions form a chelate bond with the amine group of the chitosan, the physical strength of the chitosan bead itself increases and the transition metal ion functions as a functional group, so that the adsorption reactivity to phosphates, .
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart for explaining a method of manufacturing a chitosan bead for phosphorus removal according to an embodiment of the present invention; FIG.
2 is a graph showing the results of isothermal equilibrium adsorption experiments on chitosan beads for phosphorus removal according to the present invention, chitosan beads according to the prior art, and commercial anion exchange resins.
3 is a graph showing the phosphate removal efficiency of the chitosan beads for phosphorus removal according to the present invention prepared using nickel chloride hydrate.
The present invention provides a technique for improving the adsorption reactivity of chitosan beads to phosphate and increasing the physical strength of chitosan beads.
Specifically, in preparing chitosan beads by using chitosan powder, transition metal ions act as a cross-linking agent between the chitosan polymers, and at the same time, the immobilized transition metal ions function as a functional group of phosphate, Thereby enhancing the strength of the beads and enhancing the adsorption reactivity with respect to the phosphate.
The chitosan powder has an amine group (-NH 2 ), and the transition metal ion forms chelate bonds with an amine group (-NH 2 ). This means that the chitosan polymer constituting the chitosan bead constitutes a chelate bond and the physical strength of the chitosan bead is increased by the chelate binding force. On the other hand, the transition metal ion forming the chelate bond functions as a functional group and is capable of ligand bonding with a phosphate, which is a ligand in water. Thus, the chelate bond between the transition metal ion and the amine group can increase the strength of the chitosan bead and enable the phosphate adsorption.
Hereinafter, the chitosan beads for removing phosphorus according to an embodiment of the present invention and a method for producing the same will be described in detail.
Referring to FIG. 1, a chitosan solution is first prepared (S101). The chitosan solution can be prepared by dissolving the chitosan powder in an acid solution. Chitosan powder is a deacetylation material of chitin and has an amine group (-NH 2 ) on its surface. The chitosan polymer constituting the chitosan powder has a polysaccharide amine group having a linear structure of a glucosamine unit. As the acid solution, a hydrochloric acid solution is applicable. For the strength of chitosan beads, the concentration of the chitosan solution is preferably about 1 to 3 wt%.
Then, the chitosan solution is titrated with an aqueous solution of sodium hydroxide (NaOH) to prepare chitosan beads (S102). That is, the chitosan solution is dropped into the aqueous solution of sodium hydroxide by one drop to be cured in a bead form.
In a state where chitosan beads are prepared, a transition metal hydrate aqueous solution is prepared, and chitosan beads are charged into the transition metal hydrate aqueous solution and stirred to induce chelate bonds between amine groups and transition metal ions provided in the chitosan (S103). The transition metal hydrate used in the transition metal hydrate aqueous solution may be a hydrate of a compound containing a transition metal. In one embodiment, cupric chloride (CuCl 2 .2H 2 O) or nickel chloride hydrate (NiCl 2 .6H 2 O ) Can be used.
(N 2 ) of the amine group (-NH 2 ) in the chitosan and the copper ion (Cu 2+ ) in the aqueous solution are added to the aqueous solution of cupric chloride (CuCl 2 .2H 2 O) Is formed through the Lewis acid base reaction. That is, a chelate bond is formed between the amine group (-NH 2 ) of the chitosan and the copper ion (Cu 2+ ), which means that the chitosan polymer is connected in a chain form via the copper ion (Cu 2+ ). The copper ions (Cu 2+ ), which is a chelate bond with the amine group (-NH 2 ) of chitosan, that is, the transition metal ion, functions as a crosslinking agent for the chitosan polymer and functions as a functional group capable of ligand binding with phosphate in water (functional group).
In order to increase the strength and the phosphate adsorption reactivity of chitosan beads, the amount of copper ion (Cu 2+ ) which forms a chelate bond with the amine group (-NH 2 ) of chitosan must be maximized. To this end, cupric chloride (CuCl 2 · 2H 2 O) should be mixed and dissolved in distilled water at a high concentration of 1 to 2 wt%. When the amount is less than 1 wt%, the amount of unreacted amine group (-NH 2 ) increases. When the amount exceeds 2 wt%, the amount of copper ions (Cu 2+ ) forming a chelate bond with the amine group (-NH 2 ) .
In order to maximize the chelate bonding reaction during the mixing reaction of the chitosan beads and the transition metal hydrate aqueous solution, it is preferable to maintain the pH of the aqueous solution at 4 to 5. The aqueous solution 4 less than the bonding force between the hydrogen ions (H +) is increased by an amine group (-NH 2) a copper ion (Cu 2+) instead of the hydrogen ion (H +) is improved in the Keeping a low pH aqueous solution of The protonation of the amine group is promoted, which weakens the chelate bond between the amine group and the copper ion. In addition, when the pH of the aqueous solution becomes neutral or basic, OH - is increased in the aqueous solution, and the generated OH - reacts with copper ions (Cu 2+ ) to precipitate copper.
On the other hand, when the nickel chloride hydrate (NiCl 2 .6H 2 O) is applied, when chitosan beads are added to the nickel chloride hydrate (NiCl 2 .6H 2 O) and stirred, the amine group (-NH 2 ) nitrogen (N) and nickel ions in the aqueous solution (Ni 2+) forms the chelating bond, an amine group (-NH 2) and forming a nickel ion chelate binding of chitosan (Ni 2+) carrying out the crosslinking agent role of chitosan polymer And functions as a functional group capable of underwater phosphate and ligand binding.
In order to increase the strength and the phosphate adsorption reactivity of chitosan beads like copper ion (Cu 2+ ), the amount of nickel ion (Ni 2+ ) that forms a chelate bond with the amine group (-NH 2 ) of chitosan must be maximized. For sufficient isothermal adsorption, nickel chloride hydrate (NiCl 2 .6H 2 O) should be mixed and dissolved in distilled water at a concentration of 0.2 wt% or more. Considering that precipitation of nickel occurs at a concentration of 0.6 wt% or more, nickel chloride hydrate (NiCl 2 .6H 2 O) solution is in the optimum range of 0.2 to 0.6 wt%. In addition, the pH of the aqueous solution should be maintained at 5-7 to maximize the chelation reaction.
Experimental examples of the method for producing chitosan beads for phosphorus removal according to an embodiment of the present invention and characteristics of the chitosan beads produced according to the present invention will now be described.
Experimental Example 1: Production of chitosan beads for phosphorus removal using cupric chloride hydrochloride [
5 g of chitosan powder having an amine group (-NH 2 ) was prepared. The chitosan powder was deacetylated 70-80% from chitin. 5 g of chitosan powder was mixed with 200 mL of 1 vol% HCl solution for 12 hours to prepare a 2.5 wt% chitosan solution. Then, 2.5 wt% chitosan solution was titrated into 1M NaOH solution to prepare chitosan beads. At this time, the NaOH solution was slowly stirred to titrate the chitosan solution to keep the concentration of NaOH constant and prevent the entangled chitosan beads from being entangled, and then slowly stir for 3 hours for sufficient reaction. The synthesized chitosan beads were then washed several times with distilled water.
3 g of cupric chloride (CuCl 2 .2H 2 O) was dissolved in 200 mL of distilled water to prepare a 1.5 wt% aqueous cupric chloride solution. Then, the washed chitosan beads were mixed in the cupric chloride aqueous solution to prepare 24 Lt; / RTI > When there was a change in pH during the mixing process, the pH of the cupric chloride aqueous solution was maintained at 5 using 0.1 M HCl or 0.1 M NaOH solution. After mixing for 24 hours, the chitosan beads were washed with distilled water, some were stored in distilled water in gel form, and some were dried at the laboratory temperature.
<Experimental Example 2: Isothermal equilibrium adsorption test>
The chitosan beads (CB-Cu in FIG. 2) of the present invention prepared in Experimental Example 1, the chitosan beads to which GLA (Gamma-Linolenic Acid) 'CB-G-Cu') and commercial anion exchange resin ('AMP16' in Fig. 2).
Three sets of PO 4 3- aqueous solutions (first set, second set, third set) having different concentrations (0-100 mg / l L as PO 4 3- ) contained in 10 50 ml were prepared. In each set, each concentration of PO 4 3- aqueous solution contains nitrate and sulfate in concentrations of 100 mg / L, in addition to phosphate (PO 4 3- ).
0.05 g of chitosan bead (CB-Cu) of Example 1 was added to each of the first set of aqueous solutions and chitosan beads (CB-G-Cu) added with GLA were added to each of the second set of aqueous solutions, And 0.05 g of commercial anion exchange resin (AMP16). In this state, each vessel was stirred at 30 rpm for 48 hours. The pH was maintained at 7.5 ± 0.2 using 0.1 M HCl and 0.1 NaOH at 2, 6, 12, 20, and 48 hours to maintain constant pH.
As shown in FIG. 2, the adsorption efficiency of chitosan beads (CB-Cu) prepared in Example 1 at all the equilibrium concentrations was higher than that of chitosan beads (CB-G-Cu) Is increased. In the case of chitosan beads (CB-G-Cu) using GLA as a cross-linking agent, the amount of copper ions immobilized in chitosan beads is small, suggesting that phosphate adsorption efficiency is low. In addition, it can be confirmed that the chitosan bead (CB-Cu) prepared in Example 1 has a higher adsorption rate of phosphorus than the commercial anion exchange resin (AMP16).
<Experimental Example 3: Preparation of chitosan beads for phosphorus removal using nickel chloride hydrate>
Chitosan beads synthesized through Experimental Example 1 were prepared.
1 g of nickel chloride hydrate (NiCl 2 .6H 2 O) was dissolved in 200 mL of distilled water to prepare a 0.5 wt% nickel chloride hydrate aqueous solution. Then, the chitosan beads synthesized in Experimental Example 1 were mixed in the nickel chloride hydrate aqueous solution, Lt; / RTI > When there was a change in pH during the mixing process, the pH of the nickel chloride hydrate aqueous solution was maintained at 6 by using 0.1 M HCl or 0.1 M NaOH solution. After mixing for 24 hours, the chitosan beads were washed with distilled water, some were stored in distilled water in gel form, and some were dried at the laboratory temperature.
<Experimental Example 4: Efficiency of removing ginseng salt>
Chitosan beads (CB-Ni-gel, CB-Ni-dry) prepared in Experimental Example 3 and chitosan beads (CB) not containing nickel were subjected to phosphate removal experiments.
3, the chitosan beads CB containing no nickel had a phosphate removal rate of 5% or less, while the gel-type chitosan beads CB-Ni-gel and CB- Ni-dry) showed a phosphate removal rate of over 70%. In addition, the phosphate removal rate of dried chitosan beads (CB-Ni-dry) shows higher performance.
Claims (13)
Curing the chitosan solution to form chitosan beads; And
Mixing the chitosan beads with the transition metal hydrate aqueous solution to induce a chelate bond between the transition metal ion and the amine group,
Wherein the chitosan polymer is crosslinked by the transition metal ion by the chelate bond between the transition metal ion and the amine group and acts as a functional group capable of ligand bonding of the transition metal ion.
Wherein the chitosan solution is titrated with a NaOH solution to form chitosan beads.
The amine group forms a chelate bond with the transition metal, and the chitosan polymer is crosslinked by the transition metal ion by the chelate bond of the transition metal ion and the amine group, and the transition metal ion acts as a functional group capable of ligand bonding. Chitosan beads for removal.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190124859A (en) * | 2018-04-27 | 2019-11-06 | 전북대학교산학협력단 | Cationic barrier adsorbent and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190124859A (en) * | 2018-04-27 | 2019-11-06 | 전북대학교산학협력단 | Cationic barrier adsorbent and method for preparing the same |
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