KR20160113374A - Method for preparing polyacrylonitrile fiber adsorbent and adsorbent thereof - Google Patents

Method for preparing polyacrylonitrile fiber adsorbent and adsorbent thereof Download PDF

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KR20160113374A
KR20160113374A KR1020150037608A KR20150037608A KR20160113374A KR 20160113374 A KR20160113374 A KR 20160113374A KR 1020150037608 A KR1020150037608 A KR 1020150037608A KR 20150037608 A KR20150037608 A KR 20150037608A KR 20160113374 A KR20160113374 A KR 20160113374A
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adsorbent
fiber
polyacrylonitrile fiber
group
amine group
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KR1020150037608A
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Korean (ko)
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윤영상
윤성일
김석
박상원
조철웅
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전북대학교산학협력단
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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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • B01J20/3282—Crosslinked polymers

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  • Organic Chemistry (AREA)
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a manufacturing method of a polyacrylonitrile fiber type adsorbent having a fast rate of adsorption in comparison to a conventional ion exchange resin while having a simple manufacturing process, and to an adsorbent thereby. Provided is a fiber type adsorbent having excellent adsorption performance without a manufacturing process of polymerizing monomers. Also, the fiber type adsorbent includes: an internal support layer having high mechanical strength; and an outer coating layer having a plurality of cationic functional groups, wherein the outer coating layer surrounds the internal support layer.

Description

TECHNICAL FIELD The present invention relates to a method for preparing a polyacrylonitrile fiber type adsorbent,

The present invention relates to a method for producing a polyacrylonitrile fiber type adsorbent and an adsorbent therefor, and more particularly, to a method for producing a polyacrylonitrile fiber type adsorbent having a faster adsorption rate and a simpler manufacturing process than a conventional ion exchange resin, ≪ / RTI >

In order to remove or recover the metal ions in the solution, precipitation, adsorption (including ion exchange), filtration and liquid-liquid extraction are used. Among them, the ion exchange method has advantages of simple process and great energy efficiency, and is mainly used in a low concentration ion condition. Ion exchange resin, which is mainly used in ion exchange, has been researched and developed since the 1930s, and has various kinds and high adsorption amounts depending on the application. However, ion exchange resins cause a volume increase or decrease in throughput of the continuous process at slow adsorption rates. Recently, the ion exchange fiber has a structure in which a polymer matrix exists in the fiber and a high concentration of functional groups are implanted in the matrix. These ion exchange fibers mainly have adsorption functional groups on the surface thereof and have a faster adsorption rate than ion exchange resins. Using ion exchange fibers with fast adsorption rates can increase the efficiency of the process, such as volume reduction and increased adsorption throughput. However, since most high-strength and high-performance ion exchange fibers are produced by graft copolymerization, they are difficult to manufacture and have a high production cost. In order to improve the process of using the ion exchange material and the efficiency of the manufacturing process, there is a need for an easier ion exchange fiber production method.

[Patent Literature]

Korean Patent Publication No. 10-2014-0019379

The present invention provides a fibrous adsorbent material having a faster adsorption rate than the conventional ion exchange resin.

The present invention provides a fibrous adsorbent material excellent in strength and adsorption capacity.

The present invention provides a fibrous adsorbent material having a simple manufacturing process and a low manufacturing cost.

One aspect of the present invention is

Hydrolyzing the polyacrylonitrile fiber to produce a carboxyl group on the surface thereof;

Adding the fiber to an amine group-containing cationic polymer solution to react; And a step of adding a cross-linking agent after the completion of the reaction, followed by stirring. The present invention also relates to a method for producing a polyacrylonitrile fiber-type adsorbent.

In another aspect, the present invention relates to a polyacrylonitrile fiber having a carboxyl group formed on its surface; And an amine group-containing cationic polymer layer bridged over the fiber surface, wherein the fibers form an inner support of the adsorbent, wherein the amine group-containing cationic polymer layer is a fiber- The surface of which is coated with a polyacrylonitrile fiber-type adsorbent comprising an outer layer formed by adsorption reaction between a carboxyl group formed on the fiber surface and an amine group of the polymer.

INDUSTRIAL APPLICABILITY The present invention can provide a fibrous adsorbent excellent in adsorption performance without a process for copolymerization of monomers. In addition, the adsorbent of the present invention has high mechanical strength and adsorption rate because it is formed of an inner supporting layer having high mechanical strength and a coating layer having a plurality of cationic functional groups surrounding it.

1 is a schematic view of a fibrous adsorbent of the present invention.
Fig. 2 shows a process for producing the fibrous adsorbent of the present invention.
Figures 3 and 4 show hydrolysis of the polyacrylonitrile fibers to produce carboxyl groups on the surface.
Fig. 5 is an analysis of FT-IR of Example 1, Comparative Example 1 and Comparative Example 2. Fig.
6 compares the adsorption amounts of Example 1 and Comparative Examples 1 and 2.
Figure 7 shows the adsorbent performance of Example 1 according to hydrolysis time.
Figure 8 shows the adsorption amounts and rate constants of Example 1 and the commercial ion exchange resin in a batch process.
FIG. 9 shows the adsorption amounts and rate constants of Example 1 and commercial ion exchange resins in a continuous process using the Thomas model.

Hereinafter, the present invention will be described in more detail.

1 is a schematic view of a fibrous adsorbent of the present invention. Fig. 2 shows a process for producing the fibrous adsorbent of the present invention. Figure 3 shows hydrolysis of the polyacrylonitrile fibers to produce carboxyl groups on the surface.

1 to 3, the fibrous adsorbent of the present invention comprises a polyacrylonitrile fiber 10 forming an inner support layer and an amine group-containing cationic polymer layer 20 surrounding it.

The polyacrylonitrile fiber 10 is an inner support, and a carboxyl group is formed on its surface.

The polyacrylonitrile fiber may be a known product. The polyacrylonitrile fibers may have a strength of 1 to 12 cN / dtex.

The polyacrylonitrile fiber has a cyanide group.

2 and 3, the production method of the present invention hydrolyzes the polyacrylonitrile fiber to produce a carboxyl group on its surface. That is, the present invention hydrolyzes polyacrylonitrile fibers to convert a cyano group to a carboxyl group.

The hydrolysis can be performed by adding the polyacrylonitrile fiber to an acid solution or an alkali solution and then stirring.

There is no particular limitation on the acid solution or alkali solution. FIG. 3 shows a hydrolysis reaction when polyacrylonitrile fibers are added to an alkali solution, and FIG. 4 shows a hydrolysis reaction when polyacrylonitrile fibers are added to an acid solution.

The following formulas 2 and 3 represent the hydrolysis reaction.

Figure pat00001

Figure pat00002

The concentration of the acid or alkali solution to be added in the hydrolysis reaction may range from 3 to 10M. The temperature of the hydrolysis reaction may be 40 to 80 ° C. and the reaction time may be 30 to 150 minutes.

Referring to FIG. 2, the reaction step is a step of reacting the fiber with an amine group-containing cationic polymer solution.

More specifically, the reaction step is a step in which an adsorption reaction between the carboxyl group formed on the fiber surface and the amine group of the polymer is performed. The pH of the reaction step can be adjusted to 5 to 11, preferably 9.5 to 10.5. In the above pH range, the carboxylic group of the fiber has a negative charge and the amine of the cationic polymer has a positive charge, so that an adsorption reaction can occur between them.

The amine group-containing cationic polymer may be selected from the group consisting of polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene oxide, polymer of dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate and vinylpyrrolidone A linear polymer of epichlorohydrin and dimethylamine, polydialyldimethylammonium chloride, polyethanolamine / methyl chloride, and modified polyethyleneimine. The copolymer may be at least one selected from the group consisting of:

The reaction step coating the fiber surface with the amine group-containing cationic polymer through the adsorption reaction.

The reaction step is a step of mixing the fiber and the amine group-containing cationic polymer at a ratio of 1: 0.01 to 10 (w: w).

The method of the present invention includes a step of adding a crosslinking agent and stirring after the above-mentioned reaction step. The crosslinking agent may be at least one selected from the group consisting of glutaraldehyde, isocyanide derivatives, epichlorohydrin, and bisdiazobenzidine.

  The crosslinking agent can enhance the chemical bonding between the fibers as the inner support layer and the cationic polymer as the outer coating layer surrounding the fibers.

When the crosslinking agent is treated, the crosslinking agent may be mixed in a solution state in an amount of 0.01 to 0.5% (v / v) relative to the mixture of the fiber and the amine group-containing cationic polymer, preferably 0.02 to 0.1% v).

As the solvent, at least one selected from the group consisting of water, alcohols such as methanol, chloroform, pyridine, ethanol, and butanol may be used.

The fibrous adsorbent produced in the present invention comprises a polyacrylonitrile fiber having a carboxyl group on its surface and an amine group-containing cationic polymer layer crosslinked and coated on the surface of the fiber.

Wherein the fiber forms an inner support of the adsorbent and the amine group-containing cationic polymer layer forms an outer layer by coating the surface of the fiber as an inner support, wherein the coating comprises a carboxyl group formed on the fiber surface, Is formed by an adsorption reaction between amine groups.

The adsorbent may further include a crosslinking agent coated on the surface of the amine group-containing cationic polymer layer.

The adsorbent is capable of adsorbing an anionic oil-soluble metal, a heavy metal, and a rare metal at a pH of 6 or less.

The adsorbent may have a strength of 1 to 10 cN / dtex, and the adsorption rate may be 20 times or more that of the ion exchange resin.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but they should be construed as merely illustrative of preferred embodiments of the present invention, and the examples do not limit the scope of the present invention.

Example  One

2 g of polyacrylonitrile fibers (Bluestar, 12k) were stirred in 5 M NaOH solution at 80 DEG C for 35-180 minutes. 0.2 g of the hydrolyzed polyacrylonitrile fiber was reacted by stirring in 200 ml polyethyleneimine solution (mulberry product, concentration: 13 g / L) for 4 hours. Subsequently, 0.5 ml of glutaraldehyde was added and the mixture was stirred for 3 hours to obtain a polyacrylonitrile adsorbent (PWPAN) coated with polyethyleneimine. During the coating reaction, the pH of the solution was adjusted to 10.5.

Comparative Example  One

The known polyacrylonitrile fibers (WPAN) were used without any special treatment.

Comparative Example  2

The known polyacrylonitrile fibers were used after hydrolysis under the same conditions as in Example 1 (denoted as HWPAN)

Fig. 5 is an analysis of FT-IR of Example 1, Comparative Example 1 and Comparative Example 2. Fig. Referring to FIG. 5, the polyacrylonitrile fiber (Comparative Example 1) had a large peak (C≡N) peak at 2241 cm -1 and no peak at 3000 cm -1. The hydrolyzed polyacrylonitrile fiber (Comparative Example 2) had a peak of 2241 cm-1 cyanide disappearing and a hydroxyl group (OH) peak at 3100 cm-1 or higher and a carbonyl (C = O) peak. This indicates that hydrolysis converts the cyan group to a carboxyl group. The polyacrylonitrile fibers coated with polyethyleneimine (Example 1) exhibited primary, secondary and tertiary amine peaks at 2851 cm-1, 2941 cm-1 and 3338 cm-1, respectively, Coating.

Experiment 1: Adsorption amount evaluation

Adsorption evaluation method: K2PtCl6 was dissolved in a 0.1 M HCl solution to prepare a 500 mg / L solution of Pt concentration. To 30 ml of this solution was added 0.03 g of the adsorbent material of Example 1, Comparative Examples 1 and 2 which had been dried, and the mixture was stirred at 25 rpm for 24 hours at 160 rpm. The concentration of the solution before and after the adsorption was measured by ICP-AES and the adsorption amount was calculated using the following material knowledge.

Figure pat00003

6 compares the adsorption amounts of Example 1 and Comparative Examples 1 and 2. Referring to FIG. 6, Comparative Example 1 and Comparative Example 2 showed an adsorption amount of almost 0 mg / g, whereas the adsorbent of Example 1 showed a adsorption performance of Pt of 148.89 mg / g.

Figure 7 shows the adsorbent performance of Example 1 according to hydrolysis time. Referring to FIG. 7, the change in adsorption amount with increasing hydrolysis time increased with increasing hydrolysis time until 120 minutes, and then decreased with 180 minutes. This is because the carboxyl group is increased by hydrolysis until 120 minutes, and then the carboxyl group is decreased by excessive hydrolysis and the efficiency of polyethyleneimine coating is lowered.

Experiment 2: Evaluation of adsorption rate (batch type)

Adsorption evaluation method: 0.1 g of the adsorbent prepared in Example 1 was added to 250 ml of a 500 mg / L solution of Pt prepared in 0.1 M HCl solution, and the concentration of the solution was analyzed for 7 hours. The adsorbent was compared with a commercial ion exchange resin, LEWATIT MonoPlus M 500 (Lanxess), for comparative evaluation. The analytical method and the adsorption amount calculation method are the same as the above adsorption amount evaluation method. The kinetic evaluation model used a pseudo-first-order model and a pseudo-second-order model, and the results are shown in FIG. 8 and Table 1.

Figure pat00004

Referring to FIG. 8 and Table 1, the adsorption rate constants (k1, k2) of both models are higher than those of the commercial ion exchange resin of Example 1, and thus the adsorption rate can be confirmed fast. Referring to the more accurate pseudo-second-order results, the adsorbent of Example 1 showed a 370-fold higher adsorption rate than commercial ion exchange resins. This is because the adsorbing functional groups of the developed material exist in the cationic polymer coated on the surface, and the diffusion distance to be adsorbed is very short. Referring to FIG. 8, it can be confirmed that the time for reaching the maximum adsorption amount of 140 mg / g of Pt is about 3 minutes in the case of Example 1, but more than 10 minutes is required for the commercial ion exchange resin.

Experiment 3 Adsorption rate evaluation (continuous process)

Evaluation method: 0.7854 ml of adsorbent was filled in a chromatography column (006SCC-10-10-FF, Omnifit), and a 250 mg / L solution of Pt prepared with 0.1 M HCl was flowed at 3 ml / min. (Retention time: 0.2618 min).

The adsorption amounts and rate constants were measured using the Thomas model and are shown in FIG. 9 and Table 2. Referring to FIG. 9 and Table 2, in the commercial ion exchange resin, 50 mgL or more of Pt was leached from the initial 5 minutes, but the developed material showed excellent adsorption performance due to outflow of Pt of 5 mg / L or more from 36 minutes.

The continuous adsorption process currently used in the commercial process is carried out at a residence time of 10 to 15 minutes or more. This condition is due to the use of an ion exchange resin with a slow processing speed. Since the adsorbent of the present invention has a fast adsorption rate, it can be used under a smaller residence time.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Those skilled in the art will readily appreciate that various changes, modifications, and variations may be made without departing from the spirit and scope of the present invention, as defined by the following claims and accompanying drawings.

Claims (11)

Hydrolyzing the polyacrylonitrile fiber to produce a carboxyl group on the surface thereof;
Adding the fiber to an amine group-containing cationic polymer solution to react; And
And adding the cross-linking agent after the completion of the reaction and stirring the resultant polyacrylonitrile fiber-type adsorbent. The polyacrylonitrile fiber type adsorbent according to claim 1, wherein the hydrolysis is a step of adding the polyacrylonitrile fiber to an acid solution or an alkali solution, followed by stirring at 30 to 90 ° C. Way. The method of claim 1, wherein the reaction step comprises adsorption reaction between a carboxyl group formed on a fiber surface and an amine group of the polymer. [Claim 4] The method according to claim 3, wherein the reaction step comprises coating the polyacrylonitrile fiber surface with the amine group-containing cationic polymer through the adsorption reaction, Gt; The method for producing a polyacrylonitrile fiber-type adsorbent according to claim 1, wherein the reaction step comprises mixing the fiber and the amine group-containing cationic polymer at a ratio of 1: 0.01 to 10 (w: w). The method of claim 1, wherein the pH of the reaction step is adjusted to a range of 5 to 11. [3] The method according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of glutaraldehyde, isocyanide derivatives, epichlorohydrin, and bisdiazobenzidine Wherein the polyacrylonitrile fiber type adsorbent is a polyacrylonitrile fiber type adsorbent. The method of claim 1 wherein the amine group-containing cationic polymer is selected from the group consisting of polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene oxide, dimethylaminoethyl methacrylate polymer, and dimethylaminoethyl methacrylate Characterized in that it is at least one selected from the group of copolymers of vinylidene chloride and vinylpyrrolidone, linear polymers of epichlorohydrin and dimethylamine, polydiallyldimethylammonium chloride, polyethanolamine / methyl chloride and modified polyethyleneimine (Method for producing polyacrylonitrile fiber type adsorbent). A polyacrylonitrile fiber having a carboxyl group on its surface;
An adsorbent comprising an amine group-containing cationic polymer layer crosslinked on the fiber surface, the fibers forming an inner support of the adsorbent, wherein the amine group-containing cationic polymer layer is formed on the fiber surface To form an outer layer, wherein the coating comprises adsorption reaction between a carboxyl group formed on the fiber surface and an amine group of the polymer. The adsorbent according to claim 9, wherein the adsorbent further comprises a cross-linking agent coated on the surface of the amine group-containing cationic polymer layer. The polyacrylonitrile fiber type adsorbent according to claim 9, wherein the adsorbent adsorbs an anionic oil-soluble metal at a pH of 6 or less.



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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180106542A (en) * 2017-03-21 2018-10-01 한국원자력연구원 Fabrication method of ion exchange fiber using crosslinking by radiation
CN115440404A (en) * 2021-06-03 2022-12-06 西南科技大学 Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using novel functional fibers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180106542A (en) * 2017-03-21 2018-10-01 한국원자력연구원 Fabrication method of ion exchange fiber using crosslinking by radiation
CN115440404A (en) * 2021-06-03 2022-12-06 西南科技大学 Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using novel functional fibers
CN115440404B (en) * 2021-06-03 2024-04-26 西南科技大学 Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using functionalized fibers

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